CN1319854C - Spherical silicon dioxide granule preparation method - Google Patents
Spherical silicon dioxide granule preparation method Download PDFInfo
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- CN1319854C CN1319854C CNB2005100001518A CN200510000151A CN1319854C CN 1319854 C CN1319854 C CN 1319854C CN B2005100001518 A CNB2005100001518 A CN B2005100001518A CN 200510000151 A CN200510000151 A CN 200510000151A CN 1319854 C CN1319854 C CN 1319854C
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 235000012239 silicon dioxide Nutrition 0.000 title claims description 22
- 239000008187 granular material Substances 0.000 title description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 132
- 239000002245 particle Substances 0.000 claims abstract description 58
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000004005 microsphere Substances 0.000 claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 239000004793 Polystyrene Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 229920002223 polystyrene Polymers 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 230000032683 aging Effects 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- GODZNYBQGNSJJN-UHFFFAOYSA-N 1-aminoethane-1,2-diol Chemical compound NC(O)CO GODZNYBQGNSJJN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 28
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 21
- 238000004945 emulsification Methods 0.000 claims description 20
- 230000003750 conditioning effect Effects 0.000 claims description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- 239000000839 emulsion Substances 0.000 claims description 11
- 239000003995 emulsifying agent Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 4
- 210000003097 mucus Anatomy 0.000 claims description 4
- 239000008188 pellet Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 230000001186 cumulative effect Effects 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 2
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 19
- 230000001804 emulsifying effect Effects 0.000 abstract description 14
- 239000011148 porous material Substances 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- -1 alkoxy silane Chemical compound 0.000 abstract 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 230000006837 decompression Effects 0.000 abstract 1
- 235000011167 hydrochloric acid Nutrition 0.000 abstract 1
- 125000001165 hydrophobic group Chemical group 0.000 abstract 1
- 150000001455 metallic ions Chemical class 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 229910000077 silane Inorganic materials 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000002454 metastable transfer emission spectrometry Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
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- Silicon Compounds (AREA)
Abstract
The present invention relates to a preparation method for a spherical silica particle, which comprises: alkoxy silane is dissolved in acetone; deionized water and concentrated hydrochloric acids are added to the acetone to polymerize at the temperature of 80 to 100DEGC to obtain slimy liquid; the obtained slimy liquid is distilled by decompression and then dissolved in acetone or ethanol solution in which polystyrene microspheres with unitary particle diameter are dispersed; the slimy liquid is emulsified in an emulsifying device; ammonia water, organic amine and alcohol amine or glycol amine are added to the slimy liquid to generate silica microspheres; the silica microspheres are filtered out, treated by aging, washed and then incandesced for 3 to 5 hours at the temperature of 500 to 700DEGC to obtain the spherical silica particle. In the method, a surface group regulating agent can also be added in the polymerization procedure. The method has the advantages of short polymerization time, no need of nitrogen protection and simple experiment conditions; the particle diameters of the microspheres of the obtained product are homogeneous, and the pore diameter can be modified within a wide range by adopting polystyrene microspheres with different particle diameters; hydrophobic groups of methyl or ethyl, etc. can be introduced to the surfaces of the microspheres; no metal salt ions are introduced, and therefore, the spherical silica particle can be used on occasions which have high requirements for metallic ion impurities.
Description
Technical field
The present invention relates to a kind of preparation method of preparing spherical SiO 2 particles, specifically relate to the preparation method of the adjustable preparing spherical SiO 2 microballoon of a kind of function aperture, particle diameter and surface group.
Background technology
The silicon dioxide microsphere of function aperture and adjustable grain is because it has obtained the attention of researcher height in application prospects aspect medicine controlled releasing, Industrial Catalysis and the efficient liquid phase chromatographic stuffing.At present existing multiple comparatively sophisticated silicon dioxide microsphere preparation method: 1) spray-drying process 2) accumulation microballoon method 3) the Sol-Gel method.In the spray-drying process, the particle diameter of thus obtained microsphere directly is subjected to the influence of nozzle atomization effect, is difficult to realize evenly.General its product needs further size grading.Pile up silicon ball method and can't obtain the uniform grading product equally.The Sol-Gel method is the common method of preparation mono-dispersion microballoon, as document 1:Journal of Colloid Interface Science 26, and report among the 62-69 (1968), ST BER uses NH
3Hydrolysis TEOS (tetraethoxysilane) prepares the method for monodisperse silica microspheres, but its product cut size is difficult to reach more than 2 microns, and will use high density ammoniacal liquor even liquefied ammonia in the process.At document 2:Journal of Colloid Interface Science 180, among the 237-241 (1996), Dong Peng has obtained the silicon dioxide granule of greater particle size by adding the silicon sol seed and adding the method that NaCl suppresses homogeneous nucleation, but still can not obtain the particle more than 2 microns.Because 1 micron to 50 microns is the required microspherulite diameter of high efficiency chromatography commonly used, so these methods are had little scope for one's talents at the high efficiency chromatography surface side filler.At document 3:Porous Silica, Elsevier, Amsterdam, 1979, among the 147-163, Unger has reported the method for preparing porous silica silica gel with the water glass acidifying, but owing to adopt water glass as the silicon source, making has a certain amount of inorganic ion can't flush away in the product, limited the use of product.In the Chinese patent of publication number CN1318514A, Yang Xin stands and discloses the first acid catalysis TEOS hydrolytic polymerization of using, and add the method that alkali or organic amine prepare high pure spherical silica gel again, yet the experiment condition that this method adopts in the hydrolytic polymerization step is comparatively harsh, needs N
2Protection, and reaction need high-speed stirring in this external its balling-up step, otherwise product cut size was difficult for homogenizing and refinement more than 20 hours under 120 ℃, this has all brought certain difficulty to suitability for industrialized production.
Summary of the invention
The objective of the invention is to overcome that prior art is difficult to obtain during preparing spherical SiO 2 particles evenly in preparation, particle diameter reaches the product more than 2 microns, and the defective that experiment condition is comparatively harsh, thereby provide a kind of function aperture, particle diameter and surface group adjustable, and the preparation method of the preparing spherical SiO 2 particles of mild condition.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of preparation method of preparing spherical SiO 2 particles, comprise following step:
1) polymerization: organoalkoxysilane is dissolved in the acetone, stirs adding deionized water and concentrated hydrochloric acid down, form mixed solution, the add-on of acetone is 1～2 times of organoalkoxysilane volume, HCl and H
2The add-on of O is respectively 0.01～0.1 times and 0.4～1.8 times of molar weight of organoalkoxysilane; Mixed solution is kept little boiling under 57～60 ℃, boil off acetone, be warming up to 80～100 ℃ of polymerization for some time, under the catalysis of hydrochloric acid, make organoalkoxysilane generation polymerization; With gained mucus under the vacuum tightness of 10～20mmHg, 140～150 ℃ of underpressure distillation to be to remove monomer and oligopolymer; Gained liquid is dissolved in the acetone or alcohol solution, or gained liquid is dissolved in the acetone or alcohol solution that is dispersed with the single particle size polystyrene microsphere of 8～40wt% (preparation of polystyrene microsphere sees document 4 for details: functional polymer journal .1993.006 (001) .-12-20), and the size of functional hole in the particle diameter of the polystyrene microsphere decision product microballoon;
Described organoalkoxysilane is 1～3 kind the mixture that is selected from tetramethoxy-silicane, tetraethoxysilane or the tetrapropoxysilane;
2) balling-up: the acetone or alcohol solution that step 1) is obtained places the film emulsifier unit to carry out emulsification, and the foreign minister is the aqueous acetone solution of 0～40v%, the used particle diameter that sees through the aperture decision product pellet of film; Emulsion after the film emulsification under agitation adds proper ammonia, organic amine, hydramine or glycol amine, the silicon dioxide microsphere that is produced leached, and ageing 24 hours in deionized water, then use ethanol and washing with acetone respectively; The microballoon of gained 500～700 ℃ of following calcinations 3～5 hours, is just obtained the silicon dioxide microsphere of particle diameter of the present invention and function even aperture distribution.
The preparation method of preparing spherical SiO 2 particles provided by the invention also can add the surface group conditioning agent, comprises following step:
1) polymerization: organoalkoxysilane is dissolved in the acetone, add the surface group conditioning agent, stir and add deionized water and concentrated hydrochloric acid down, form mixed solution, wherein the add-on of surface group conditioning agent is 0.1～1 times (mol ratio) of organoalkoxysilane presoma, the add-on of acetone is organoalkoxysilane presoma and surface group conditioning agent cumulative volume 1～2 times, and the add-on of HCl is 0.01～0.1 times (mol ratio) of organoalkoxysilane presoma and surface group conditioning agent total amount, H
2The add-on of O is 0.4～1.8 times (mol ratio) of organoalkoxysilane presoma and surface group conditioning agent total amount; Mixed solution is kept little boiling under 57～60 ℃, boil off acetone, be warming up to 80～100 ℃ of polymerization for some time, under the catalysis of hydrochloric acid, make the mixture generation polymerization of organoalkoxysilane and surface group conditioning agent; With gained mucus under the vacuum tightness of 10～20mmHg, 140～150 ℃ of underpressure distillation to be to remove monomer and oligopolymer; Gained liquid is dissolved in the acetone or alcohol solution, or gained liquid is dissolved in the acetone or alcohol solution that is dispersed with the single particle size polystyrene microsphere of 8～40wt% (preparation of polystyrene microsphere sees document 4 for details: functional polymer journal .1993.006 (001) .-12-20), and the size of functional hole in the particle diameter of the polystyrene microsphere decision product microballoon;
Described organoalkoxysilane is 1～3 kind the mixture that is selected from tetramethoxy-silicane, tetraethoxysilane or the tetrapropoxysilane;
Described surface group conditioning agent is to be selected from methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane or the ethyl triethoxysilane one or more;
2) balling-up: the acetone or alcohol solution that step 1) is obtained places the film emulsifier unit to carry out emulsification, and the foreign minister is the aqueous acetone solution of 0～40v%, the used particle diameter that sees through the aperture decision product pellet of film; Emulsion after the film emulsification under agitation adds proper ammonia, organic amine, hydramine or glycol amine, the silicon dioxide microsphere that is produced leached, and ageing 24 hours in deionized water, then use ethanol and washing with acetone respectively; With the silicon dioxide microsphere of O for toluene gained, molten its inner polystyrene microsphere that goes, vacuum-drying then just obtains the silicon dioxide microsphere of particle diameter of the present invention and function even aperture distribution and area load organic group.
Stand in the Chinese patent of publication number CN1318514A disclosed method with Yang Xin and compare, the advantage of method provided by the invention is:
1, the catalyst levels of hydrolysing step employing is bigger, makes polymerization time shorten, and temperature descends; Saved nitrogen protection, experiment condition is simple.
2, adopted the film emulsifying technology in the balling-up stage, because the aperture of employed inorganic porous ceramic film is even, makes the particle diameter of particle in the gained emulsion also very even, thus the particle diameter that makes product microballoon homogenizing greatly, saved requirement, be beneficial to the serialization industrial production more high-speed stirring.
3, the highly homogeneous phenylethylene micro ball of particle diameter is applied to make in the balling-up system thus obtained microsphere inside function hole of aperture homogeneous has been arranged, and the aperture can be by the polystyrene microsphere that adopts different-grain diameter in very wide scope modulation.This is highly beneficial to being used in the future medicine controlled releasing research.
4, the present invention has also introduced the surface group conditioning agent in polymerization procedure, makes the surface of microspheres product introduce hydrophobic groupings such as methyl or ethyl, and this is significant for special chromatographic separation system.
5, do not introduce any ionizable metal salt in present method, can satisfy the occasion that impurity metal ion is had higher requirements.
Embodiment
Embodiment 1,
The tetraethoxysilane (TEOS) of 10ml after underpressure distillation is dissolved in the 20ml acetone, stirs the concentrated hydrochloric acid (mol (HCl)/mol (TEOS)=0.068 that adds 0.75ml deionized water (0.47) and 0.3ml 37% (wt) down; Mol (H2O)/mol (TEOS)=1.17), the mixed solution of formation stirs 10min post-heating to 60 ℃, and the mild stirring guarantee system is little to boil about 1 hour to boil off acetone.System is warming up to 80 ℃ kept 3 hours, under the catalysis of hydrochloric acid, make organoalkoxysilane generation polymerization, this liquid is placed under 140 ℃, 20mmHg vacuum tightness, boil off TEOS monomer and oligomer.System is dissolved in acetone with it after reducing to normal temperature, obtains 10ml solution, places the film emulsifier unit to carry out emulsification this solution, the foreign minister is the aqueous acetone solution of 50ml10v%, the mean pore size of emulsifying film is 800nm, and gas-operated pressure is 0.1MPa, 40 ℃ of emulsifying temperatures.Stir and in this emulsion after the film emulsification, add 2ml ammoniacal liquor (27%wt) down, the silicon dioxide microsphere that is produced is leached, and ageing 24 hours in deionized water, leach after acetone and washing with alcohol, the oven dry back obtains the high pure spherical silica particle of 10 microns of particle diameters in 550 ℃ of following calcinations 4 hours.
Embodiment 2,
The tetraethoxysilane (TEOS) of 20ml after underpressure distillation is dissolved in the 30ml acetone, stirs adding 1.5ml deionized water and the 0.6ml 37% (concentrated hydrochloric acid of wt (mol (HCl)/mol (TEOS)=0.068 down; Mol (H
2O)/mol (TEOS)=1.17), the mixed solution of formation stirs 10min post-heating to 60 ℃, and the mild stirring guarantee system is little to boil about 1 hour to boil off acetone.System is warming up to 90 ℃ kept 4 hours, under the catalysis of hydrochloric acid, make organoalkoxysilane generation polymerization, this liquid is placed under 140 ℃, 10mmHg vacuum tightness, boil off TEOS monomer and oligomer.System is dissolved in it in acetone of the polystyrene microsphere that is dispersed with 1.5g particle diameter 300nm after reducing to normal temperature, obtain 20ml solution, place the film emulsifier unit to carry out emulsification this solution, the foreign minister is the aqueous acetone solution of 100ml 20v%, the mean pore size of emulsifying film is 800nm, gas-operated pressure is 0.08MPa, 50 ℃ of emulsifying temperatures.Stir and in this emulsion after the film emulsification, add 5ml ammoniacal liquor (27%wt) down, the silicon dioxide microsphere that is produced is leached, and ageing 24 hours in deionized water, leach after acetone and washing with alcohol, the oven dry back obtains 12 microns of particle diameters and inner high pure spherical silica particle with diameter 300nm hole in 600 ℃ of following calcinations 4 hours.
Embodiment 3,
40ml is dissolved in the 100ml acetone through the Union carbide A-162 (MTES) of underpressure distillation through tetraethoxysilane after the underpressure distillation (TEOS) and 10ml, stir the concentrated hydrochloric acid (mol (HCl)/mol (TEOS+MTES)=0.066, the mol (H that add 4ml deionized water and 1.5ml 37% (wt) down
2O)/mol (TEOS+MTES)=1.2), the mixed solution of formation stirs 10min post-heating to 60 ℃, and the mild stirring guarantee system is little to boil about 1 hour to boil off acetone.System is warming up to 100 ℃ kept 4 hours, under the catalysis of hydrochloric acid, make organoalkoxysilane generation polymerization, this liquid is placed under 150 ℃, 10mmHg vacuum tightness, boil off monomer and oligomer.System is dissolved in it in acetone of the polystyrene microsphere that is dispersed with 2.8g particle diameter 150nm after reducing to normal temperature, obtain 40ml solution, place the film emulsifier unit to carry out emulsification this solution, the foreign minister is the aqueous acetone solution of 200ml 20v%, the mean pore size of emulsifying film is 1 micron, gas-operated pressure is 0.06MPa, 30 ℃ of emulsifying temperatures.Stir and in this emulsion after the film emulsification, add 15ml ammoniacal liquor (27%wt) down, the silicon dioxide microsphere that is produced is leached, and ageing 24 hours in deionized water, leach after acetone and washing with alcohol, soak the silicon dioxide microsphere 48 hours of gained with 50ml60 ℃ toluene, molten its inner polystyrene microsphere that goes, vacuum-drying then obtains the high pure spherical porous silica particle that 20 microns of particle diameters, surface have methyl.
Embodiment 4,
The tetramethoxy-silicane (TMOS) of 50ml after underpressure distillation is dissolved in the 100ml acetone, stirs the concentrated hydrochloric acid (mol (HCl)/mol (TMOS)=0.01, the mol (H that add 10ml deionized water and 0.3ml 37% (wt) down
2O)/mol (TMOS)=1.8), the mixed solution of formation stirs 10min post-heating to 60 ℃, and the mild stirring guarantee system is little to boil about 1 hour to boil off acetone.System is warming up to 100 ℃ kept 4 hours, under the catalysis of hydrochloric acid, make organoalkoxysilane generation polymerization, this liquid is placed under 150 ℃, 10mmHg vacuum tightness, boil off TMOS monomer and oligomer.System is dissolved in acetone with it after reducing to normal temperature, obtains 50ml solution, places the film emulsifier unit to carry out emulsification this solution, the foreign minister is the aqueous acetone solution of 200ml 20v%, the mean pore size of emulsifying film is 1 micron, and gas-operated pressure is 0.06MPa, 40 ℃ of emulsifying temperatures.Stir and in this emulsion after the film emulsification, add 15ml ammoniacal liquor (27%wt) down, the silicon dioxide microsphere that is produced is leached, and ageing 24 hours in deionized water, leach after acetone and washing with alcohol, the oven dry back obtains the preparing spherical SiO 2 particles of 21 microns of particle diameters in 600 ℃ of following calcinations 4 hours.
Embodiment 5,
20ml is dissolved in the 100ml acetone through the ethyl trimethoxy silane (ETMS) of underpressure distillation through tetramethoxy-silicane after the underpressure distillation (TMOS) and 20ml, stir the concentrated hydrochloric acid (mol (HCl)/mol (TMOS)=0.1 that adds 0.25ml deionized water and 2.4ml 37% (wt) down, mol (H2O)/mol (TMOS)=0.4), the mixed solution that forms stirs 10min post-heating to 60 ℃, and the mild stirring guarantee system is little to boil about 1 hour to boil off acetone.System is warming up to 100 ℃ kept 4 hours, under the catalysis of hydrochloric acid, make organoalkoxysilane generation polymerization, this liquid is placed under 150 ℃, 10mmHg vacuum tightness, boil off monomer and oligomer.System is dissolved in it in acetone of the polystyrene microsphere that is dispersed with 2.0g particle diameter 100nm after reducing to normal temperature, obtain 40ml solution, place the film emulsifier unit to carry out emulsification this solution, the foreign minister is the aqueous acetone solution of 150ml 30v%, the mean pore size of emulsifying film is 1 micron, gas-operated pressure is 0.05MPa, 40 ℃ of emulsifying temperatures.Stir and in this emulsion after the film emulsification, add 10ml ammoniacal liquor (27%wt) down, the silicon dioxide microsphere that is produced is leached, and ageing 24 hours in deionized water, leach after acetone and washing with alcohol, soak the silicon dioxide microsphere 48 hours of gained with 40ml60 ℃ of toluene, molten its inner polystyrene microsphere that goes, vacuum-drying then obtains the high pure spherical porous silica particle that 18 microns of particle diameters, surface have methyl.
Embodiment 6,
Get the tetrapropoxysilane (TPOS) of 20ml after underpressure distillation and be dissolved in the 30ml acetone, stir the concentrated hydrochloric acid (mol (HCl)/mol (TPOS)=0.1, the mol (H that add 0.83ml deionized water and 0.7ml 37% (wt) down
2O)/mol (TPOS)=1.0), the mixed solution of formation stirs 10min post-heating to 60 ℃, and the mild stirring guarantee system is little to boil about 1 hour to boil off acetone.System is warming up to 100 ℃ kept 4 hours, under the catalysis of hydrochloric acid, make organoalkoxysilane generation polymerization, this liquid is placed under 150 ℃, 10mmHg vacuum tightness, boil off monomer and oligomer.System is dissolved in acetone with it after reducing to normal temperature, obtains 20ml solution, places the film emulsifier unit to carry out emulsification this solution, the foreign minister is the aqueous acetone solution of 50ml 30v%, the mean pore size of emulsifying film is 1 micron, and gas-operated pressure is 0.06MPa, 40 ℃ of emulsifying temperatures.Stir and in this emulsion after the film emulsification, add 10ml ammoniacal liquor (27%wt) down, the silicon dioxide microsphere that is produced is leached, and ageing 24 hours in deionized water, leach after acetone and washing with alcohol, the oven dry back obtains the high pure spherical silica particle of 25 microns of particle diameters in 600 ℃ of following calcinations 4 hours.
Claims (7)
1, a kind of preparation method of preparing spherical SiO 2 particles comprises following step:
1) polymerization: organoalkoxysilane is dissolved in the acetone, stirs adding deionized water and concentrated hydrochloric acid down, form mixed solution; Mixed solution is kept little boiling under 57～60 ℃, boil off acetone, be warming up to 80～100 ℃ of polymerization for some time, under the catalysis of hydrochloric acid, make organoalkoxysilane generation polymerization; With gained mucus under the vacuum tightness of 10～20mmHg, 140～150 ℃ of underpressure distillation to be to remove monomer and oligopolymer; Gained liquid is dissolved in the acetone or alcohol solution;
2) balling-up: the acetone or alcohol solution that step 1) is obtained places the film emulsifier unit to carry out emulsification, and the foreign minister is the aqueous acetone solution of 0～40v%, the used particle diameter that sees through the aperture decision product pellet of film; Emulsion after the film emulsification under agitation adds ammoniacal liquor, organic amine, hydramine or glycol amine, the silicon dioxide microsphere that is produced leached, and ageing 24 hours in deionized water, then use ethanol and washing with acetone respectively; The microballoon of gained 500～700 ℃ of following calcinations 3～5 hours, is just obtained the silicon dioxide microsphere of particle diameter and function even aperture distribution.
2, the preparation method of preparing spherical SiO 2 particles as claimed in claim 1 is characterized in that: the organoalkoxysilane in the described step 1) is 1～3 kind the mixture that is selected from tetramethoxy-silicane, tetraethoxysilane or the tetrapropoxysilane.
3, the preparation method of preparing spherical SiO 2 particles as claimed in claim 1 is characterized in that: the add-on of acetone is 1～2 times of organoalkoxysilane volume in the described step 1), HCl and H
2The add-on of O is respectively 0.01～0.1 times and 0.4～1.8 times of molar weight of organoalkoxysilane.
4, the preparation method of preparing spherical SiO 2 particles as claimed in claim 1, it is characterized in that: when being dissolved in gained liquid in the acetone or alcohol solution in the described step 1), be dispersed with the single particle size polystyrene microsphere of 8～40wt% in the described acetone or alcohol.
5, a kind of preparation method of preparing spherical SiO 2 particles comprises following step:
1) polymerization: organoalkoxysilane is dissolved in the acetone, adds the surface group conditioning agent, stir and add deionized water and concentrated hydrochloric acid down, form mixed solution, wherein the add-on of surface group conditioning agent is 0.1～1 times of organoalkoxysilane molar weight; Mixed solution is kept little boiling under 57～60 ℃, boil off acetone, be warming up to 80～100 ℃ of polymerization for some time, under the catalysis of hydrochloric acid, make the mixture generation polymerization of organoalkoxysilane and surface group conditioning agent; With gained mucus under the vacuum tightness of 10～20mmHg, 140～150 ℃ of underpressure distillation to be to remove monomer and oligopolymer; Gained liquid is dissolved in the acetone or alcohol solution, or gained liquid is dissolved in the acetone or alcohol solution that is dispersed with the single particle size polystyrene microsphere of 8～40wt%;
Described surface group conditioning agent is to be selected from methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane or the ethyl triethoxysilane one or more;
2) balling-up: the acetone or alcohol solution that step 1) is obtained places the film emulsifier unit to carry out emulsification, and the foreign minister is the aqueous acetone solution of 0～40v%, the used particle diameter that sees through the aperture decision product pellet of film; Emulsion after the film emulsification under agitation adds ammoniacal liquor, organic amine, hydramine or glycol amine, the silicon dioxide microsphere that is produced leached, and ageing 24 hours in deionized water, then use ethanol and washing with acetone respectively; With the silicon dioxide microsphere of O for toluene gained, molten its inner polystyrene microsphere that goes, vacuum-drying then just obtains the silicon dioxide microsphere of particle diameter and function even aperture distribution and area load organic group.
6, the preparation method of preparing spherical SiO 2 particles as claimed in claim 5 is characterized in that: the organoalkoxysilane in the described step 1) is 1～3 kind the mixture that is selected from tetramethoxy-silicane, tetraethoxysilane or the tetrapropoxysilane.
7, the preparation method of preparing spherical SiO 2 particles as claimed in claim 5, it is characterized in that: the add-on of the acetone in the described step 1) is organoalkoxysilane and surface group conditioning agent cumulative volume 1～2 times, the add-on of HCl is organoalkoxysilane and surface group conditioning agent molar weight total amount 0.01～0.1 times, H
2The add-on of O is organoalkoxysilane and surface group conditioning agent molar weight total amount 0.4～1.8 times.
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| CN100406381C (en) * | 2006-09-06 | 2008-07-30 | 湖北大学 | Functional bionic Nano particles of silicon dioxide, and prepartion method |
| CN100372763C (en) * | 2006-10-30 | 2008-03-05 | 复旦大学 | Synthetic method for porous silicon dioxide hollow micro ball |
| CN100532256C (en) * | 2007-10-25 | 2009-08-26 | 同济大学 | Method of producing hollow silicon dioxide microsphere with mercapto on internal and external surfaces |
| WO2011063392A2 (en) * | 2009-11-23 | 2011-05-26 | 3M Innovative Properties Company | Methods of surface treating porous particles |
| CN101913611B (en) * | 2010-03-17 | 2012-05-02 | 上海大学 | Method for preparing simple, convenient, size-controllable and mono-disperse nano silicon dioxide granules |
| CN102557044B (en) * | 2010-12-16 | 2015-02-11 | 中国石油化工股份有限公司 | Method for preparing macroporous silica microsphere |
| CN102704273B (en) * | 2012-07-06 | 2014-01-15 | 陕西科技大学 | Preparation method of polyacrylic ester/hollow silicon dioxide nanometer composite leather finishing agent |
| CN108892144B (en) * | 2018-06-22 | 2021-09-28 | 南京亘闪生物科技有限公司 | Preparation method of functionalized porous particle size monodisperse silicon dioxide spherical material |
| US20220153936A1 (en) * | 2019-02-22 | 2022-05-19 | Zhejiang Third Age Material Technology Co., Ltd | Preparation Method For Spherical Or Angular Powder Filler, Spherical Or Angular Powder Filler Obtained Thereby, And Application Thereof |
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| CN1351958A (en) * | 2000-11-15 | 2002-06-05 | 中国科学院大连化学物理研究所 | Process for preparing high purity microspheric uniform pore size silica gel for high efficiency liquid phase chromatography |
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| 膜乳化－液中干燥法制备单分散高分子微球 包德才，高等学校化学学报，第25卷第7期 2004 * |
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