CN102115089A - Preparation method of micron grade mono-dispersive silicon dioxide microspheres - Google Patents

Preparation method of micron grade mono-dispersive silicon dioxide microspheres Download PDF

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CN102115089A
CN102115089A CN2009102641502A CN200910264150A CN102115089A CN 102115089 A CN102115089 A CN 102115089A CN 2009102641502 A CN2009102641502 A CN 2009102641502A CN 200910264150 A CN200910264150 A CN 200910264150A CN 102115089 A CN102115089 A CN 102115089A
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solution
preparation
silicon dioxide
tetraethoxysilane
micron order
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夏明珠
赵贝贝
雷武
田彩华
王风云
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Nanjing University of Science and Technology
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Abstract

The invention discloses a preparation method of micron grade mono-dispersive silicon dioxide microspheres. The method comprises the following steps of: (1) uniformly mixing ammonia water, a solvent and ultrapure water according to a certain proportion to obtain hydrolysate, wherein the ammonia water serves as a catalyst, and the solvent is ethanol or acetone; (2) dissolving a tetraethoxysilane solution in the solution prepared in the step (1) and hydrolyzing and condensing tetraethoxysilane by uniformly stirring to generate a silicon dioxide crystal nucleus; (3) continuously dropwise adding the hydrolysate obtained in the step (1) and the tetraethoxysilane solution into the silicon dioxide crystal nucleus solution prepared in the step (2) respectively to allow the silicon dioxide crystal nucleus to grow gradually; and (4) making the solution obtained in the step (3) react by stirring in an enclosed state, standing, precipitating, performing suction filtration and separation on white precipitates at the bottom of a container under a reduced pressure, repeatedly washing with ethanol and acetone until the precipitates are neutral, and drying to obtain a target product, namely micron grade mono-dispersive silicon dioxide microspheres. The preparation method is simple and practicable, has lower cost and high batch repeatability, and can be used for preparing silicon dioxide microspheres with uniform spheres form and high monodispersity.

Description

The preparation method of micron order monodispersive silica microballoon
Technical field
The present invention relates to the silicon dioxide microsphere technology, particularly a kind of preparation method of micron order monodispersive silica microballoon.
Background technology
Silicon dioxide microsphere is easy to easily advantage such as modification of control, surface with its physical properties such as size distribution, pore structure, specific surface area, be widely used in fields such as slow releasing carrier of medication, support of the catalyst, photonic crystal, high-performance ceramic, and the optimal selection of high performance liquid chromatography stationary phase matrix, dental filler, liquid-crystal display polarizing coating pad etc. especially of monodispersity micron silica microballoon.According to its know-why, the preparation method of silicon dioxide microsphere can be divided into four classes: (1) polymerisation induced coacervation of colloid method; (2) sol-gel method; (3) spray-drying process; (4) emulsion method, but preparation technology is loaded down with trivial details, and repeatability etc. is still stubborn problem between the shape control of silicon dioxide microsphere, size distribution, each batch.
Figure G2009102641502D00011
Deng adopting sol-gel method first, under the ammonia katalysis, the tetraethoxysilane hydrolytic condensation become nano level monodispersive silica microballoon, but this method be difficult to prepare the micron order microballoon (
Figure G2009102641502D00012
W, FinkA.Controlled growth of monodisperse silica spheres in the micron size range, Journalof Colloid and Interface Science, 1968,26:62～69).Unger etc. at first make the silicon-dioxide nucleus, again with the utmost point slowly speed drip the alcoholic solution of silicon source solution and ammoniacal liquor, the silicon-dioxide nucleus is slowly grown, make 0.05～10 μ m atresia monodisperse silica microspheres.For preventing that new karyomorphism from becoming, the rate of addition of silicon source solution is extremely slow, the process of growth of 3 μ m monodispersive silica microballoons reaches 5 days (Unger K, Giesche H, Kinkel J, Spherical SiO 2Particles, US 4775520,1988).David reduces nucleation elementary reaction temperature, generate big nucleus earlier, the nucleus growth stage then at room temperature finishes, the above silicon dioxide microsphere particle size distribution range of 2.5 μ m of this method preparation is wide, microballoon is polymolecularity (Anderson D J, Lawn O, Process for forming large silica spheres by low temperature nucleation, US5425930,1995).Chang and Lee have proposed silicon-dioxide nucleus diauxic growth model, the relation of nucleation process and system degree of supersaturation has been discussed, proposed to obtain the required condition of monodispersity microballoon, but the maximum monodispersity microspherulite diameter of its preparation only is 1 μ m (Sang Mok Chang; Minhyung Lee; Woo-Sik Kim, Preparation of large monodispersed spherical silica particles using seed particlegrowth.Journal of colloid and interface science, 2005,286,536).
Summary of the invention
The object of the present invention is to provide a kind of method for preparing micron order monodispersive silica microballoon, this preparation method is simple, cost is lower, batch between good reproducibility, its prepared silicon dioxide microsphere that goes out is spherical evenly, monodispersity is good.
The technical solution that realizes the object of the invention is: the preparation method of micron order monodispersive silica microballoon of the present invention may further comprise the steps:
(1) ammoniacal liquor, solvent, ultrapure water are mixed in proportion, be mixed with hydrolyzed solution, wherein ammoniacal liquor is catalyzer, and solvent is ethanol or acetone;
(2) tetraethoxysilane solution is dissolved in the solution of step (1) preparation, evenly stirs and make the tetraethoxysilane hydrolytic condensation, generate the silicon-dioxide nucleus;
(3) in the silicon-dioxide nucleus solution of step (2) preparation, drip hydrolyzed solution and the tetraethoxysilane solution that step (1) makes respectively continuously, the silicon-dioxide nucleus is grown up gradually;
(4) step (3) gained solution is carried out airtight stirring reaction and leaves standstill heavyization, container bottom white precipitate decompress filter is separated, and extremely neutral with ethanol, acetone repetitive scrubbing, and drying obtains target product micron order monodispersive silica microballoon.
The present invention compared with prior art, its remarkable advantage: (1) adopts sol-gel method, at first the catalytic hydrolysis tetraethoxysilane obtains the silicon-dioxide nucleus under cold condition, add tetraethoxysilane and hydrolyzed solution with certain speed respectively again, make initial nucleus grow gradually and effectively prevent and secondary nucleation from finally making the micron silica microballoon; (2) the monodispersive silica microspherulite diameter maximum that makes of this method can reach 5 μ m, and microspherulite diameter Tile Width index is little, and monodispersity is good; (3) operation is simple, conditions such as controlled temperature, stirring velocity, proportioning raw materials, the good reproducibility between each batch.
Description of drawings
Fig. 1 prepares the schematic flow sheet of micron order monodispersive silica microballoon for the present invention.
Fig. 2 makes the silicon dioxide microsphere infrared spectrogram for the embodiment of the invention 1.
The polymolecularity silicon dioxide microsphere stereoscan photograph that Fig. 3 makes for the embodiment of the invention 1.
The median size that Fig. 4 makes for the embodiment of the invention 2 is the polymolecularity silicon dioxide microsphere stereoscan photograph of 1.6 μ m.
The median size that Fig. 5 makes for the embodiment of the invention 3 is the monodispersive silica microballoon stereoscan photograph of 2.6 μ m.
The median size that Fig. 6 makes for the embodiment of the invention 4 is the monodispersive silica microballoon stereoscan photograph of 2.3 μ m.
The median size that Fig. 7 makes for the embodiment of the invention 5 is the monodispersive silica microballoon stereoscan photograph of 2.8 μ m.
The median size that Fig. 8 makes for the embodiment of the invention 6 is the monodispersive silica microballoon stereoscan photograph of 1.0 μ m.
The median size that Fig. 9 makes for the embodiment of the invention 7 is the monodispersive silica microballoon stereoscan photograph of 4.8 μ m.
The median size that Figure 10 makes for the embodiment of the invention 8 is the monodispersive silica microballoon stereoscan photograph of 3.2 μ m.
Embodiment
Below in conjunction with accompanying drawing the present invention is described in further detail.
(1) ammoniacal liquor, solvent, ultrapure water are mixed in proportion, be mixed with hydrolyzed solution, wherein ammoniacal liquor is catalyzer, and solvent is ethanol or acetone;
(2) a certain amount of tetraethoxysilane solution is dissolved in the above-mentioned solution, evenly stir and make the tetraethoxysilane hydrolytic condensation, generate the silicon-dioxide nucleus, 1～10 ℃ of temperature of reaction, reaction times 5～10min, stirring velocity 200～300rpm, the TEOS massfraction is 20～30% in total system, the solvent quality mark is 5～10%, and the quality mark is 50～60%, and the ammonia massfraction is 10～15%;
(3) each constituent mass mark is constant in the total system of maintenance, in above-mentioned silicon-dioxide nucleus solution, drip hydrolyzed solution and TEOS solution continuously with certain speed respectively, the silicon-dioxide nucleus is grown up gradually, 10～30 ℃ of temperature of reaction, continue joining day 0.5～5h, stirring velocity 180～250rpm;
(4) airtight stirring reaction 10～16h leaves standstill heavyization 4～10h, there-necked flask bottom white precipitate decompress filter is separated, and extremely neutral with ethanol, acetone repetitive scrubbing, drying obtains target product micron order monodispersive silica microballoon.
Embodiment 1
62.73mL ammoniacal liquor (massfraction 25%), 14.62mL ethanol, 33.25mL ultrapure water (handling through Milli-Q) are mixed, be mixed with hydrolyzed solution; Under the 280rpm magnetic agitation, 5mL hydrolyzed solution and 2mLTEOS are joined in the clean 250mL there-necked flask, under 30 ℃ of water bath with thermostatic control conditions, react, approximately behind the 5min, mixing solutions becomes single-phase oyster white suspension liquid, SiO by colourless two-phase 2Nucleus forms.Change the magnetic agitation rotating speed then to 200rpm, keep 30 ℃ constant, adopt syringe pump in nucleus solution, to drip pure ammonia solution and TEOS continuously with the speed of 0.5mL/min, 0.2mL/min respectively, nucleus is slowly grown, dropping time 2h with the airtight stirring reaction 16h of system, leaves standstill heavyization 4h.At last bottom white precipitate decompress filter is separated, and extremely neutral with ethanol, acetone repetitive scrubbing, and 110 ℃ of following dry 16h promptly get final reacting product.Fig. 2 has shown that the characteristic frequency of specimen group distributes 504cm -1The place is Si-O-Si flexural vibration, 799cm -1The O-Si-O of place flexural vibration, 952cm -1The place is Si-OH stretching vibration, 1103cm -1The place is Si-O-Si stretching vibration, 1638cm -1The place is the stretching vibration of N-H primary amine, 3443cm -1The place is H-O-H stretching vibration, wherein 1103cm -1The place is the strongest for the Si-O-Si stretching vibration peak, 504cm -1Taking second place for Si-O-Si flexural vibration peak in the place, shows to exist a large amount of bridging oxygens to exist in the sample, generated silicon-dioxide in the proved response.Microspherulite diameter is tangible quadratic distribution, and big microspherulite diameter reaches 4 μ m, and the minimicrosphere particle diameter only is 0.5 μ m, and the particle diameter distribution width index reaches 1.60, as shown in Figure 3.
Embodiment 2
Adopt and embodiment 1 identical hydrolyzed solution, under the 280rpm magnetic agitation, 5mL hydrolyzed solution and 2mL TEOS are joined in the clean 250mL there-necked flask, under 20 ℃ of water bath with thermostatic control conditions, react, approximately behind the 8min, mixing solutions becomes single-phase oyster white suspension liquid, SiO by colourless two-phase 2Nucleus forms.Change the magnetic agitation rotating speed then to 200rpm, keep 20 ℃ constant, adopt and embodiment 1 identical drips of solution add mode, dropping time 2h with the airtight stirring reaction 16h of system, leaves standstill heavyization 4h, and, obtain the SiO of median size 1.6 μ m with bottom settlings separation, washing, drying 2Microballoon still has the small-particle of a small amount of secondary nucleation in the system, the particle diameter distribution width index is 1.05, is polymolecularity, as shown in Figure 4.
Embodiment 3
Adopt and embodiment 1 identical hydrolyzed solution, and 5mL hydrolyzed solution and 2mL TEOS be precooled to 10 ℃, under the 280rpm magnetic agitation, 5mL hydrolyzed solution and 2mLTEOS are joined in the clean 250mL there-necked flask, under 10 ℃ of conditions, react, approximately behind the 5min, mixing solutions becomes single-phase oyster white suspension liquid, SiO by colourless two-phase 2Nucleus forms.Change the magnetic agitation rotating speed then to 200rpm, keep 10 ℃ constant, adopt and embodiment 1 identical drips of solution add mode, dropping time 2h, the airtight stirring reaction 16h of system, leave standstill heavyization 4h, and, obtain the monodispersity SiO of median size 2.6 μ m bottom settlings separation, washing, drying 2Microballoon, particle diameter distribution width index are 1.03, as shown in Figure 5.Comparative Examples 1, example 2 and example 3, the contriver finds, under the constant situation of other condition, along with the reduction of temperature of reaction, SiO 2Microspherulite diameter increases and monodispersity improves, and the present invention adopts 10 ℃ cold condition to help preparing the microballoon that median size is big and monodispersity is good.
Embodiment 4
Adopt and embodiment 1 identical hydrolyzed solution, and 5mL hydrolyzed solution and 1.3mL TEOS be precooled to 10 ℃, under the 280rpm magnetic agitation, pure ammonia solution and TEOS that cooling is good join in the clean 250mL there-necked flask, keep temperature-resistant, approximately behind the 10min, mixing solutions becomes single-phase oyster white suspension liquid, SiO by colourless two-phase 2Nucleus forms.Change the magnetic agitation rotating speed then to 200rpm, and adopt 20 ℃ of waters bath with thermostatic control, adopt syringe pump in nucleus solution, to drip pure ammonia solution and TEOS continuously with the speed of 0.5mL/min, 0.13mL/min respectively, nucleus is slowly grown, dropping time 2h with the airtight stirring reaction 16h of system, leaves standstill heavyization 4h, and, obtain the monodispersity SiO of median size 2.3 μ m with bottom settlings separation, washing, drying 2Microballoon, particle diameter distribution width index are 1.01, as shown in Figure 6.TEOS concentration is 20% in the system, is lower than example 3, and it is little but the monodispersity degree is better finally to make microsphere average grain diameter.
Embodiment 5
Adopt and embodiment 1 identical hydrolyzed solution, and 5mL hydrolyzed solution and 2mL TEOS be precooled to 1 ℃, under the 280rpm magnetic agitation, pure ammonia solution and TEOS that cooling is good join in the clean 250mL there-necked flask, under 1 ℃ of condition of frozen water mixing, react, approximately behind the 10min, mixing solutions becomes single-phase oyster white suspension liquid, SiO by colourless two-phase 2Nucleus forms.Change the magnetic agitation rotating speed then to 200rpm, and frozen water mix bathed be replaced by 20 ℃ of waters bath with thermostatic control, adopt and embodiment 1 identical drips of solution add mode, dropping time 2h, with the airtight stirring reaction 16h of system, leave standstill heavyization 4h, and, obtain the monodispersity SiO of median size 2.8 μ m bottom settlings separation, washing, drying 2Microballoon, particle diameter distribution width index are 1.02, as shown in Figure 7.Compare with example 2, nucleation temperature is reduced to 1 ℃ and growth temperature is identical, and it is big and monodispersity good finally to make microspherulite diameter, and the present invention adopts low nucleation temperature, to preparing big particle diameter monodispersity microballoon decisive role.
Embodiment 6
Adopt and embodiment 1 identical hydrolyzed solution, and 5mL hydrolyzed solution and 2mL TEOS be precooled to 10 ℃, under the 280rpm magnetic agitation, 5mL hydrolyzed solution and 2mL TEOS are joined in the clean 250mL there-necked flask, under 10 ℃ of conditions, react, approximately behind the 5min, mixing solutions becomes single-phase oyster white suspension liquid, SiO by colourless two-phase 2Nucleus forms.Change the magnetic agitation rotating speed then to 200rpm, keep 10 ℃ constant, adopt and embodiment 1 identical drips of solution add mode, dropping time 0.5h, the airtight stirring reaction 16h of system, leave standstill heavyization 4h, and, obtain the monodispersity SiO of median size 1.0 μ m bottom settlings separation, washing, drying 2Microballoon, particle diameter distribution width index are 1.01, as shown in Figure 8.
Embodiment 7
125.46mL ammoniacal liquor (massfraction 25%), 29.24mL ethanol, 66.5mL ultrapure water (handling through Milli-Q) are mixed, be mixed with hydrolyzed solution and be precooled to 10 ℃; Under the 280rpm magnetic agitation, 5mL hydrolyzed solution and 2mL TEOS are joined in the clean 500mL there-necked flask, under 10 ℃ of conditions, react, approximately behind the 5min, mixing solutions becomes single-phase oyster white suspension liquid, SiO by colourless two-phase 2Nucleus forms.Change the magnetic agitation rotating speed then to 200rpm, keep 10 ℃ constant, adopt and embodiment 1 identical drips of solution add mode, dropping time 4h, the airtight stirring reaction 16h of system, leave standstill heavyization 4h, and, obtain the monodispersity SiO of median size 4.5 μ m bottom settlings separation, washing, drying 2Microballoon, particle diameter distribution width index only are 1.02, as shown in Figure 9.Compare with example 3, drip time lengthening, promptly TEOS adds the total amount increase, helps preparing big particle diameter microballoon.The contriver finds to add along with TEOS the increase of total amount, and microspherulite diameter can't increase without limitation, and it is 5 μ m. that the present invention makes maximum monodispersity microspherulite diameter
Embodiment 8
62.73mL ammoniacal liquor (massfraction 25%), 14.62mL acetone, 33.25mL ultrapure water (handling through Milli-Q) are mixed, be mixed with hydrolyzed solution and be precooled to 10 ℃; Under the 280rpm magnetic agitation, 5mL hydrolyzed solution and 2mL TEOS are joined in the clean 250mL there-necked flask, under 10 ℃ of conditions, react, approximately behind the 5min, mixing solutions becomes single-phase oyster white suspension liquid, SiO by colourless two-phase 2Nucleus forms.Change the magnetic agitation rotating speed then to 200rpm, keep 10 ℃ constant, adopt and embodiment 1 identical drips of solution add mode, dropping time 2h, the airtight stirring reaction 16h of system, leave standstill heavyization 4h, and, obtain the monodispersity SiO of median size 3.2 μ m bottom settlings separation, washing, drying 2Microballoon, particle diameter distribution width index are 1.02, as shown in figure 10.Compare with example 3, the present invention also can adopt acetone to make solvent, and it is bigger to make microspherulite diameter.

Claims (6)

1. the preparation method of a micron order monodispersive silica microballoon is characterized in that may further comprise the steps:
(1) ammoniacal liquor, solvent, ultrapure water are mixed in proportion, be mixed with hydrolyzed solution, wherein ammoniacal liquor is catalyzer, and solvent is ethanol or acetone;
(2) tetraethoxysilane solution is dissolved in the solution of step (1) preparation, evenly stirs and make the tetraethoxysilane hydrolytic condensation, generate the silicon-dioxide nucleus;
(3) in the silicon-dioxide nucleus solution of step (2) preparation, drip hydrolyzed solution and the tetraethoxysilane solution that step (1) makes respectively continuously, the silicon-dioxide nucleus is grown up gradually;
(4) step (3) gained solution is carried out airtight stirring reaction and leaves standstill heavyization, container bottom white precipitate decompress filter is separated, and extremely neutral with ethanol, acetone repetitive scrubbing, and drying obtains target product micron order monodispersive silica microballoon.
2. the preparation method of micron order monodispersive silica microballoon according to claim 1, it is characterized in that in the system that ethanol or acetone solvent massfraction are 5～10%, the quality mark is 50～60% in the system, and the ammonia massfraction is 10～15% in the system.
3. the preparation method of micron order monodispersive silica microballoon according to claim 1 is characterized in that: the tetraethoxysilane massfraction is 20～30% in the system.
4. the preparation method of micron order monodispersive silica microballoon according to claim 1 is characterized in that temperature of reaction is 1～10 ℃ in the step (2), and stirring velocity is 200～300rpm.
5. the preparation method of micron order monodispersive silica microballoon according to claim 1, it is characterized in that temperature of reaction is 10～30 ℃ in the step (3), stirring velocity is 180～250rpm, and the airtight stirring reaction time is 10～16h, and leaving standstill the heavyization time is 4～10h.
6. the preparation method of micron order monodispersive silica microballoon according to claim 1 is characterized in that solution evenly drips time 0.5～5h in the step (3).
CN2009102641502A 2009-12-31 2009-12-31 Preparation method of micron grade mono-dispersive silicon dioxide microspheres Pending CN102115089A (en)

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Application publication date: 20110706