CN104003410B - A kind of preparation method of monodisperse silica microspheres - Google Patents
A kind of preparation method of monodisperse silica microspheres Download PDFInfo
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- CN104003410B CN104003410B CN201410267686.0A CN201410267686A CN104003410B CN 104003410 B CN104003410 B CN 104003410B CN 201410267686 A CN201410267686 A CN 201410267686A CN 104003410 B CN104003410 B CN 104003410B
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- ammonium chloride
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 72
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 68
- 239000010703 silicon Substances 0.000 claims abstract description 68
- 239000004005 microsphere Substances 0.000 claims abstract description 58
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 57
- 241001502050 Acis Species 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 33
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 27
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 26
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 20
- 150000002148 esters Chemical class 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000012071 phase Substances 0.000 claims description 88
- 239000003921 oil Substances 0.000 claims description 68
- 238000003756 stirring Methods 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 44
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 37
- 239000007864 aqueous solution Substances 0.000 claims description 33
- 239000008346 aqueous phase Substances 0.000 claims description 31
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 31
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 29
- -1 alkyl quaternary ammonium salts Chemical class 0.000 claims description 28
- 229910001868 water Inorganic materials 0.000 claims description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 235000019270 ammonium chloride Nutrition 0.000 claims description 19
- 238000013019 agitation Methods 0.000 claims description 18
- 239000002077 nanosphere Substances 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- LQOBMKYCRQDMTN-UHFFFAOYSA-N 3-(2-ethylphenyl)pentan-3-amine;hydrochloride Chemical compound Cl.CCC1=CC=CC=C1C(N)(CC)CC LQOBMKYCRQDMTN-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 150000001350 alkyl halides Chemical class 0.000 claims description 4
- 230000005501 phase interface Effects 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical class Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000006276 transfer reaction Methods 0.000 abstract description 3
- 230000007246 mechanism Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 33
- 239000002245 particle Substances 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000006227 byproduct Substances 0.000 description 12
- 239000003814 drug Substances 0.000 description 11
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 10
- 238000010792 warming Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 102000004190 Enzymes Human genes 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 241000790917 Dioxys <bee> Species 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 229910003978 SiClx Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 4
- 235000013399 edible fruits Nutrition 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000011805 ball Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000008280 blood Substances 0.000 description 3
- 210000004369 blood Anatomy 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000013270 controlled release Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009415 formwork Methods 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N 2-Methylheptane Chemical compound CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- LAIUFBWHERIJIH-UHFFFAOYSA-N 3-Methylheptane Chemical compound CCCCC(C)CC LAIUFBWHERIJIH-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- QWUGXIXRFGEYBD-UHFFFAOYSA-M ethylmercuric chloride Chemical compound CC[Hg]Cl QWUGXIXRFGEYBD-UHFFFAOYSA-M 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- PPLBPDUKNRCHGG-UHFFFAOYSA-N 1,2-dichloropentane Chemical compound CCCC(Cl)CCl PPLBPDUKNRCHGG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010030113 Oedema Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- XKXHCNPAFAXVRZ-UHFFFAOYSA-N benzylazanium;chloride Chemical compound [Cl-].[NH3+]CC1=CC=CC=C1 XKXHCNPAFAXVRZ-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- CGSVCNBINHWWFW-UHFFFAOYSA-M dimethyl-(2-phenoxyethyl)-(thiophen-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C=1C=CSC=1C[N+](C)(C)CCOC1=CC=CC=C1 CGSVCNBINHWWFW-UHFFFAOYSA-M 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Abstract
The invention discloses the preparation method of a kind of monodisperse silica microspheres, it uses quaternary ammonium salt to be phase transfer catalyst, and ammonia is catalyst, and positive esters of silicon acis is silicon source, synthesizes described silicon dioxide microsphere by two phase process.Use such scheme, the present invention uses interface method to combine the reaction of liquid liquid interface, phase transfer reaction, mechanism of catalytic reaction synthetic silica microsphere, it is provided that the manufacture new technology of nanometer grade silica, the nanometer grade silica microsphere prepared has preferable homogeneity.
Description
Technical field
The present invention relates to microsphere field, in particular, the preparation method of a kind of monodisperse silica microspheres.
Background technology
Microsphere produces and the side of life because its special size, structure and performance make it be widely used in modern industry
Aspect face, such as in new medicine field, functional porous microsphere be almost all biological medicaments and crude drug isolated and purified during
Indispensable material；Meanwhile, microsphere can reduce the toxic and side effects of medicine as the carrier of medicine sustained and controlled release, increases medicine
Effectiveness, improves the quality of medicine.In flat display field, the highly homogeneous microsphere of particle diameter can be used for controlling as sept
Liquid crystal cell is thick；Conductive gold spacer is to connect chip and the critical material of panel；The optical property utilizing microsphere is coated onto plastics microsphere
Point source can be become area source by the surface of film, is the vitals of backlight membrane group.In field of LED illumination, in LED chip
Or addition microsphere is possible not only to increase substantially LED luminous efficiency in encapsulating material, it is also possible to increase the mildness of light.Making up
Product field, interpolation microsphere, to being possible not only to increase feel and uvioresistant function in cosmetics, also can hide the defect of skin, prolong
The stability of long effective ingredient, increases the aesthetic feeling of skin.In water treatment field, functional microsphere i.e. ion exchange resin is the most extensive
Ground is for removing the impurity in water, to prepare high purity water for quasiconductor and field of medicaments.In field of blood purification, microsphere is permissible
It is used for optionally removing the harmful substance in blood, to reach the purpose of blood purification.At medical diagnostic field, magnetic and glimmering
Pumped FIR laser microsphere has been widely used in immunoassay, makes the high throughput testing of Multi-example or many targets be possibly realized.At enzyme
Catalytic field, microsphere can keep high specificity and the catalytic efficiency of enzyme as the carrier that enzyme is fixing, improves the stability of enzyme
And the life-span, reduce the enzyme pollution to product, it is achieved the serialization of production and the recycling of enzyme.In standard metering field, standard
Granule is the standard substance for metering field, can be used for Particle Size Analyzer demarcate calibration, filter material detection, the evaluation of particle,
The analysis of powder body, environmental science, the field such as research of atmospheric pollution.At agriculture field, microsphere can have as slow controlled release carrier
Effect controls the release of insecticide, increases the effectiveness of insecticide, reduces insecticide to the pollution of environment and toxicity.Lead in military affairs
Territory, micro Nano material has been widely used for stealth aircraft, anti-chemical and biological weapons etc..
Nanometer grade silica has the physicochemical characteristics that high-purity, low-density, high-specific surface area etc. are excellent, shows
Remarkable optical, electrical, hot, power, magnetic, radiate, the property such as absorption, modern medicine, contemporary optics field of liquid crystal display, biological work
Journey, cosmetics, military field, m-n are widely used.Nano silicon can carry as the microcapsule of a kind of medicine
Body, in drug controlled release field with as colloid implant.Nano silicon can have certain city as photonic crystal
Field prospect, has been widely used in field of liquid crystal display.
About the preparation of nanometer grade silica, industry mainly applies two kinds of preparation methoies: the seed law, swelling method.
Preparation method CN101913612A of silicon dioxide microsphere provides a kind of micron-sized monodisperse silica microspheres
Preparation method, the method comprising the steps of: by single dispersing SiO2Seed, NH3-H2O and low-carbon alcohols mixing are made into seed liquor, then
Add NH3/H2O/ low-carbon alcohol solution and tetraethyl orthosilicate (TEOS)/low-carbon alcohol solution react, and make TEOS hydrolysis generate
SiO2At SiO2Grow on seed outer surface, and carry out mechanical agitation and supersound process while reaction；Treat SiO2Sphere growth
After the microsphere of the required particle diameter of one-tenth, stop charging, and continue reaction until TEOS complete hydrolysis；Reaction terminate after, by reactant liquor from
Edema with the heart involved is washed and is obtained single dispersing micron SiO2Microsphere.This invention additionally provides the micron order list prepared according to described method and divides
Dissipating silicon dioxide microsphere, its mean diameter is 2～20 μm, proportion 1.7～2.0, for atresia or almost atresia SiO2Microsphere.
Preparation method CN103086381A of silicon dioxide microsphere discloses a kind of side preparing porous silica microsphere
Method.Described method includes mixing formwork structure with full sulphurated siliastic emulsion, be spray-dried, burn after prepare porous silica
Silicon microsphere, full sulphurated siliastic emulsion be organosilicon polymer or copolymer emulsion irradiated after prepare, described formwork structure is
Not including the full vulcanite emulsion of full sulphurated siliastic emulsion, the solid content in described formwork structure accounts for after mixing institute in emulsion
The ratio having solid content is 2～50%；Burning temperature is 250～1200 DEG C；The time of burning is 10～600 minutes.This invention institute
The preparation method of the porous silica microsphere stated is simple, and equipment cost is low, and the hole formed is bigger.
It is micro-that preparation method CN102115089A of silicon dioxide microsphere discloses a kind of micron grade mono-dispersive silicon dioxide
The preparation method of ball, ammonia, solvent, ultra-pure water are mixed in proportion, are configured to hydrolyzed solution by (1), and ammonia is catalyst, molten
Agent is ethanol or acetone；(2) being dissolved in the solution that step (1) is prepared by tetraethoxysilane solution, uniform stirring makes tetrem
TMOS (i.e. tetraethyl orthosilicate) hydrolytic condensation, generates crystalline silica nuclei；(3) titanium dioxide prepared to step (2) respectively
Silicon wafer core solution drips hydrolyzed solution and tetraethoxysilane solution that step (1) prepares continuously, makes crystalline silica nuclei gradually
Grow up；(4) step (3) gained solution is carried out airtight stirring reaction and stands precipitation, the decompression of container bottom white precipitate is taken out
Filter separates, and with ethanol, acetone cyclic washing to neutral, is dried to obtain target product micron grade mono-dispersive silicon dioxide microspheres.
This invention preparation method is simple, cost is relatively low, reproducible between batch, the silicon dioxide microsphere prepared is spherical uniformly,
Monodispersity is good.
But, existing following not about ammonia catalysis teos hydrolysis synthetic silica microsphere preparation method existence
Foot: silicon dioxide microsphere particle diameter cannot be the most homogeneous, is difficult to grain-size, it is difficult to synthesis nano silicon dioxide microsphere, it is impossible to
Industrialized production.
Summary of the invention
The technical problem to be solved is to provide the preparation method of a kind of new silicon dioxide microsphere.
Technical scheme is as follows: the preparation method of a kind of monodisperse silica microspheres, and it uses the quaternary ammonium salt to be
Phase transfer catalyst, ammonia is catalyst, and positive esters of silicon acis is silicon source, synthesizes described silicon dioxide microsphere by two phase process.
Preferably, described phase transfer catalyst dissolubility in biphase is all higher than one thousandth gram.
Preferably, described phase transfer catalyst dissolubility in biphase is all higher than one of percentage gram.
Preferably, described phase transfer catalyst dissolubility in biphase is all higher than 10 grams.
Preferably, described quaternary ammonium salt includes alkyl quaternary ammonium salts.
Preferably, described quaternary ammonium salt includes the alkyl quaternary ammonium salts that carbon chain lengths is more than 4.
Preferably, the carbochain total length containing side chain in described quaternary ammonium salt is less than 20 carbon atoms, in described quaternary ammonium salt
Carbon number is less than 20.
Preferably, described alkyl quaternary ammonium salts at least includes tetramethyl ammonium chloride, tetrabutylammonium chloride, tripropyl amyl group chlorination
Ammonium, tri-n-octyl methyl ammonium chloride, triethyl benzyl ammonia chloride, three amyl group ethyl ammonium chlorides, benzyl tributyl ammonium chloride wherein it
One.
Preferably, described positive esters of silicon acis at least include alkyl, alkoxyl one of them.
Preferably, described positive esters of silicon acis is four (alkoxyl-branched alkyl) esters of silicon acis.
Preferably, described positive esters of silicon acis is four (2-methoxyl group-1-Methylethyl) and/or four (ethoxybutyl) silicic acid
Ester.
Preferably, biphase oil phase and the aqueous phase of including in described two phase process, wherein, described oil phase includes water-fast having
Machine solvent.
Preferably, described oil phase includes alkane, alkyl halide or its mixture.
Preferably, described oil phase includes normal hexane or dichloromethane.
Preferably, described preparation method comprises the following steps: Step1, is dissolved in described two phase process in described silicon source
Oil phase；Step2, is placed into described catalyst and described phase transfer catalyst in reactor as the water in described two phase process
Phase, stirs and is slowly added described oil phase, for the condensation reaction that is hydrolyzed at water phase and an oil phase interface；Step3, after stirring reaction
Separate product.
Preferably, in Step1, four (2-methoxyl group-1-Methylethyl) esters of silicon acis is dissolved in normal hexane, as described oil
Phase；In Step2, ammonia and tri-n-octyl methyl ammonium chloride aqueous solution are placed in reactor as described aqueous phase, stir and drip
Add described oil phase；In Step3, products therefrom sucking filtration is centrifuged after 2 to 10 hours, washs, is dried by stirring reaction, then heats to
200 DEG C-600 DEG C, and it is incubated 5-10 hour, it is then cooled to room temperature, carries out product washing, being dried, obtain single dispersing dioxy
SiClx nanosphere.
Preferably, ammonia and tri-n-octyl methyl ammonium chloride aqueous solution, wherein, ammonia and trioctylphosphine first are loaded in a kettle.
The volume ratio of ammonium chloride aqueous solution is 4:1 to 1:4, and the mass fraction of ammonia is 26%-30%, tri-n-octyl methyl ammonium chloride water
The mass fraction of solution is 1%～6%.
Preferably, in Step1, four (2-methoxyl group-1-Methylethyl) esters of silicon acis being dissolved in normal hexane, solution concentration is
5%～80%, as described oil phase；In Step2, ammonia and tri-n-octyl methyl ammonium chloride aqueous solution are placed in reactor work
For described aqueous phase, by mechanical agitation 1-5 hour under normal temperature and pressure, drip described oil phase, its volume be described aqueous phase volume 2 to
9 times, the stir speed (S.S.) dripping described oil phase is 200rpm-600rpm；In Step3, gained was produced after 2 to 10 hours by stirring reaction
Thing sucking filtration is centrifuged, washs, is dried, and is then warming up to 200 DEG C-600 DEG C in Muffle furnace, and is incubated 5-10 hour, then cools down
To room temperature, being centrifuged product collecting, centrifuge speed is 2000rpm～10000rpm, and then product is used second alcohol and water
Washing 3 to 5 times, obtain monodisperse silica nanosphere after drying respectively.
Using such scheme, the present invention uses interface method to combine the reaction of liquid liquid interface, phase transfer reaction, catalytic reaction machine
Reason synthetic silica microsphere, it is provided that the manufacture new technology of nanometer grade silica, the nanometer grade silica microsphere of preparation
There is preferable homogeneity.
Accompanying drawing explanation
Fig. 1 is reaction rate constant and the activation energy relation schematic diagram of catalytic reaction of the present invention；
Fig. 2 is the scanning electron microscope (SEM) photograph that embodiments of the invention 1 prepare silicon dioxide microsphere；
Fig. 3 is the scanning electron microscope (SEM) photograph that embodiments of the invention 2 prepare silicon dioxide microsphere；
Fig. 4 is the scanning electron microscope (SEM) photograph that embodiments of the invention 3 prepare silicon dioxide microsphere；
Fig. 5 is the scanning electron microscope (SEM) photograph that embodiments of the invention 4 prepare silicon dioxide microsphere；
Fig. 6 is the scanning electron microscope (SEM) photograph that embodiments of the invention 5 prepare silicon dioxide microsphere；
Fig. 7 is the schematic diagram of an embodiment of preparation method of the present invention.
Detailed description of the invention
For the ease of understanding the present invention, below in conjunction with the accompanying drawings and specific embodiment, the present invention will be described in more detail.
It should be noted that be expressed " being fixed on " another element when element, it can directly on another element or therebetween
One or more element placed in the middle can be there is.When an element is expressed " connection " another element, and it can be directly to connect
Receive another element or one or more element placed in the middle can be there is therebetween.The term that this specification is used is " vertical
", " level ", "left", "right" and similar statement for illustrative purposes only.
Unless otherwise defined, this specification is used all of technology and scientific terminology are led with the technology belonging to the present invention
The implication that the technical staff in territory is generally understood that is identical.The term used in the description of the invention in this specification is simply
Describe the purpose of specific embodiment, be not intended to limit the present invention.The term "and/or" that this specification is used includes one
Individual or the arbitrary and all of combination of multiple relevant Listed Items.
Present invention aim to address ammonia catalysis teos hydrolysis synthetic silica microsphere in existing water alcohol system
Particle diameter cannot be the most homogeneous, not easy-regulating, it is impossible to the problem of industrialized production, it is provided that a kind of interface method synthetic silica microsphere
Process.One embodiment of the present of invention is, the preparation method of a kind of monodisperse silica microspheres, and it uses quaternary ammonium salt
For phase transfer catalyst, ammonia is catalyst, and positive esters of silicon acis is silicon source, synthesizes described silicon dioxide microsphere by two phase process.As
Shown in Fig. 7, silicon source in oil phase, phase transfer catalyst and catalyst in water, reacted by liquid liquid interface, phase transfer anti-
Should, catalytic reaction synthetic silica microsphere.
Described phase transfer catalyst be concurrently present in biphase in, such as, described phase transfer catalyst is concurrently present in oil phase
With in aqueous phase.Preferably, described phase transfer catalyst dissolubility in biphase is all higher than one thousandth gram.Preferably, described
Phase transfer catalyst dissolubility in biphase is all higher than one of percentage gram, and the most described phase transfer catalyst dissolves in arbitrary phase
In.Preferably, described phase transfer catalyst dissolubility in biphase is all higher than 10 grams, the most described phase transfer catalyst
It is soluble in arbitrary phase.Phase transfer catalyst allow for being concurrently present in biphase in, the present invention could be realized and each is real
Execute example.
Quaternary ammonium salt is also known as quarternary ammonium salt, and wherein four hydrogen atoms in ammonium ion are all replaced the compound formed by alkyl,
Its formula is R4N+X-, and wherein four alkyl R can be identical, it is also possible to different, X mostly is halogen anion, such as F-、Cl-、
Br-、I-Deng, it is also possible to it is acid group, such as RCOO-etc.；Such as, described quaternary ammonium salt is alkyl quaternary ammonium salts, benzyltriethylammoinium chloride
And/or 4-butyl ammonium hydrogen sulfate (TBAB), tetrabutyl ammonium bromide, tetrabutylammonium chloride and/or tricaprylmethyl chlorination (TEBA)
Ammonium etc.；Preferably, described quaternary ammonium salt includes alkyl quaternary ammonium salts.Preferably, described quaternary ammonium salt includes the alkyl that carbon chain lengths is more than 4
Quaternary ammonium salt.Preferably, the carbochain total length containing side chain in described quaternary ammonium salt is less than 20 carbon atoms, in the most described quaternary ammonium salt
Carbon number is less than 20.Such as, described alkyl quaternary ammonium salts is the chlorination ammonium salt containing alkyl；Preferably, described quaternary ammonium alkyl
Salt at least includes tetramethyl ammonium chloride, tetrabutylammonium chloride, tripropyl amyl group ammonium chloride, tri-n-octyl methyl ammonium chloride, triethyl group
Benzyl ammonium chloride, three amyl group ethyl ammonium chlorides, benzyl tributyl ammonium chloride one of them.Preferably, in described alkyl quaternary ammonium salts,
4 alkyl are identical.
Preferably, described positive esters of silicon acis at least include alkyl, alkoxyl one of them.Preferably, described positive esters of silicon acis is
Four (alkoxyl-branched alkyl) esters of silicon acis.Preferably, described positive esters of silicon acis is four (2-methoxyl group-1-Methylethyls) and/or four
(ethoxybutyl) esters of silicon acis.It should be noted that in each compound name of the present invention use bracket, content therein be in order to
Clearly state this compound, be not construed as omissible content.
Preferably, biphase oil phase and the aqueous phase of including in described two phase process, wherein, described oil phase includes water-fast having
Machine solvent.Such as, oil phase can be organic solvent, such as toluene, chloroform, acetone etc., alkane etc can also, but can not be
It is dissolved in the solvent of water.Preferably, described oil phase includes alkane, alkyl halide or its mixture.Preferably, described oil phase includes normal hexane
Or dichloromethane.It should be noted that below portion embodiment uses normal hexane to be oil phase, in actual application, can use
Alkane, alkyl halide or its mixture such as normal butane, isopentane, 3-methyl heptane, chloropropane, the example with normal hexane as oil phase is not
As the restriction for the present invention.
Preferably, described preparation method comprises the following steps: Step1, is dissolved in described two phase process in described silicon source
Oil phase；Step2, is placed into described catalyst and described phase transfer catalyst in reactor as the water in described two phase process
Phase, stirs and is slowly added described oil phase, for the condensation reaction that is hydrolyzed at water phase and an oil phase interface；Step3, after stirring reaction
Separate product.Common, silicon source is the most, then the response time is the longest.
In order to the present invention makes the statement being more readily understood and realizing, the examples below uses quaternary ammonium salt trioctylphosphine first
Ammonium chloride is phase transfer catalyst, and ammonia is catalyst, and four (2-methoxyl group-1-Methylethyl) esters of silicon acis is silicon source, passes through
Two phase process synthesizes the method for monodispersed silicon dioxide microsphere, and hydrolysis-condensation reaction occurs at water phase and an oil phase interface, it is easy to accomplish
And control.
Four (2-methoxyl group-1-Methylethyl) esters of silicon acis hydrolysis:
Condensation reaction after the hydrolysis of four (2-methoxyl group-1-Methylethyl) esters of silicon acis:
2) liquid phase reactor: liquid--liquid reaction kinetics thermodynamics is expressed
Solution system thermodynamic power credit is analysed
Solution system thermodynamics is expressed: Δ mixG=Δ mixH-T Δ mixS (constant temperature and pressure)
Liquid phase reactor kinetics is expressed:
d[{AB]/dt=Κ d [A] [B]-Κ-d [{ AB}]-Κ2[{AB]=0
Thus calculate reaction temperature T, response time t, pressure P.
Four (2-methoxyl group-1-Methylethyl) silicon in aqueous phase (W) is drawn according to molecular reaction dynamics and thermodynamic principles
Acid esters and the input amount of ammonia.
D=A [H2O]2exp(-B[H2O]1/2)
A=[C16H36O8Si]1/2(82-151[NH3]+1200[NH3]2-366[NH3]3)
B=1.05+0.523 [NH3]-0.128[NH3]2
It is thus possible to accurately calculate the input amount in silicon source and ammonia.Then according to reaction rate constant and activation energy relation meter
The input of calculation catalyst tri-n-octyl methyl ammonium chloride:
K=Ae(-E/RT)=(A1A2/A-1)e-(E1+E2-E-1)/RT
E=E1+E2-E-1
The reaction rate constant of catalytic reaction and activation energy relation are as shown in Figure 1.Above-mentioned reaction can obtain particle diameter distribution
For the monodispersed silicon dioxide nanosphere of height, wherein, silicon dioxide particle diameter, example can be controlled by simple regulation and control experiment parameter
As, within the specific limits, increasing silicon source concentration, the microspherulite diameter obtained also increases.
Above-mentioned each related embodiment, proposes one first and utilizes quaternary ammonium salt tri-n-octyl methyl ammonium chloride for phase transfer catalysis
Agent, ammonia is catalyst, and four (2-methoxyl group-1-Methylethyl) esters of silicon acis is that silicon source is by interface method synthesis single dispersing titanium dioxide
The new method of silicon microsphere.Phase transfer catalyst tri-n-octyl methyl ammonium chloride (the Methyl trioctyl that this embodiment is used
Ammonium chloride), normal hexane, dichloromethane and water all have certain dissolubility.
Preferably, in Step1, four (2-methoxyl group-1-Methylethyl) esters of silicon acis is dissolved in normal hexane, as described oil
Phase；In Step2, ammonia and tri-n-octyl methyl ammonium chloride aqueous solution are placed in reactor as described aqueous phase, stir and drip
Add described oil phase；In Step3, products therefrom sucking filtration is centrifuged after 2 to 10 hours, washs, is dried by stirring reaction, then heats to
200 DEG C-600 DEG C, and it is incubated 5-10 hour, it is then cooled to room temperature, carries out product washing, being dried, obtain single dispersing dioxy
SiClx nanosphere.
Preferably, ammonia and tri-n-octyl methyl ammonium chloride aqueous solution, wherein, ammonia and trioctylphosphine first are loaded in a kettle.
The volume ratio of ammonium chloride aqueous solution is 4:1 to 1:4, and the mass fraction of ammonia is 26%-30%, tri-n-octyl methyl ammonium chloride water
The mass fraction of solution is 1%～6%.Wherein, during mass fraction is solution, the mass fraction of solute is Solute mass and solution
Mass ratio, also refers to that in mixture, certain material mass accounts for the percentage ratio of gross mass.Preferably, in Step1, by four (2-methoxies
Base-1-Methylethyl) esters of silicon acis is dissolved in normal hexane, and solution concentration is 5%～80%, as described oil phase；In Step2, will
Ammonia and tri-n-octyl methyl ammonium chloride aqueous solution are placed in reactor as described aqueous phase, use mechanical agitation 1-under normal temperature and pressure
5 hours, dripping described oil phase, its volume is 2 to 9 times of described aqueous phase volume, it is preferred that described oil phase volume is described aqueous phase
4 to 7 times of volume；The stir speed (S.S.) dripping described oil phase is 200rpm-600rpm；In Step3, stirring reaction 2 to 10 hours
After products therefrom sucking filtration be centrifuged, wash, be dried, in Muffle furnace, be then warming up to 200 DEG C-600 DEG C, and it be little to be incubated 5-10
Time, it being then cooled to room temperature, be centrifuged product collecting, centrifuge speed is 2000rpm～10000rpm, then by product
Wash respectively 3 to 5 times with ethanol and water, put in baking oven or vacuum drying oven 80～120 degrees Celsius and be dried, obtain single dispersing
Silica nanosphere.
Such as, the step of a kind of process being condensed into silicon dioxide microsphere that is hydrolyzed with ammonia for catalyst is such as
Under:
At tri-n-octyl methyl ammonium chloride, ammonia spirit and the normal hexane of four (2-methoxyl group-1-Methylethyl) esters of silicon acis, two
During chloromethanes solution is biphase, interface method hydrolytic condensation obtains organo-polysilane granules, synthesizes single point finally by high temperature sintering
The silicon dioxide microsphere dissipated.
Wherein, ammonia and tri-n-octyl methyl ammonium chloride aqueous solution, such as, tri-n-octyl methyl ammonium chloride are loaded in a kettle.
The concentration of aqueous solution is 1%～6% (mass fraction), preferably 2%～4%；Ammonia and tri-n-octyl methyl ammonium chloride aqueous solution
Ratio is 4:1 to 1:4 (volume ratio), and preferred ratio is 2:1 to 1:2.
By mechanical agitation 1-5 hour under normal temperature and pressure, stir speed (S.S.) 200rpm-600rpm be simultaneously added dropwise four (2-methoxyl group-
1-Methylethyl) hexane solution 1-3 hour of esters of silicon acis, by mass fraction, solution concentration is 5%～80%, is preferably
30%～60%.Dropping volume is 2～9 times of the volume of ammonia and tri-n-octyl methyl ammonium chloride aqueous solution, preferably 4～7 times；
Such as, the volume of ammonia and tri-n-octyl methyl ammonium chloride aqueous solution is 100mL, four (2-methoxyl group-1-Methylethyl) esters of silicon acis
Hexane solution volume be 200～900mL；It is preferably 400～700mL.According to the amount in dropping silicon source, react 2-10 hour；
Such as, dropping silicon source is less, then the response time is shorter.Products therefrom is centrifuged after terminating, washs, is dried, then to horse by reaction
Not adding gained solid in stove, under normal pressure, temperature programming is to 200 DEG C-600 DEG C, and is incubated 5-10 hour, is then cooled to room temperature,
Being centrifuged product collecting, centrifuge speed is 2000rpm～10000rpm.Wash respectively 3 to 5 times with ethanol and water, put
Enter in baking oven 80～120 degree to be dried, obtain monodisperse silica nanosphere.Its particle diameter is water-soluble by tri-n-octyl methyl ammonium chloride
The concentration of liquid, ammonia concn, dropping silicon source amount and stir speed (S.S.) control, and such as, silicon source concentration is the biggest, and silicon spherolite footpath is the biggest,
This is the major influence factors controlling particle diameter；Ammonia concn is the biggest, and microspherulite diameter is the least；Stir speed (S.S.) is the biggest, the particle diameter of microsphere
The least；Phase transfer catalyst, other conditions are constant, and tri-n-octyl methyl ammonium chloride concentration is the biggest, and microspherulite diameter is the least.These microspheres
Particle diameter experiment can be used to determine, the most additionally limit at this.
Such as, loading 40ml strong aqua ammonia in a kettle., 1.6g tri-n-octyl methyl ammonium chloride and 60ml water, under normal temperature and pressure
500rpm mechanical agitation 1 hour.Then limit is stirred 400ml dissolved with 100g tetra-(2-methoxyl group-1-Methylethyl) esters of silicon acis
Normal hexane, dichloromethane solution, wherein, normal hexane is 1:1 with the mol ratio of dichloromethane, drips and adds in aqueous solution, often in 1 hour
Normal temperature and pressure stirring reaction 2 hours, is centrifuged products therefrom, washs, is dried.
Then adding gained white solid in Muffle furnace, heating schedule is: first at the uniform velocity rose from room temperature in 1.5 hours
To 300 DEG C；It is then passed through 2 hours, at the uniform velocity rises to 400 DEG C from 200 DEG C；It is then passed through 1.5 hours, at the uniform velocity rises to 500 from 400 DEG C
℃；It is incubated 6 hours at 500 DEG C；Finally naturally cool to room temperature, i.e. obtain monodisperse silica Nano microsphere.
Being observed as under sweep electron microscope by prepared silica spheres, its scanning electron microscope (SEM) photograph is as in figure 2 it is shown, tie
Fruit shows, monodisperse silica sphere particle particle diameter prepared by the present invention is 277nm.
And for example, loading 60ml strong aqua ammonia in a kettle., 2.4g tri-n-octyl methyl ammonium chloride and 60ml water, under normal temperature and pressure
400rpm mechanical agitation 1.5 hours.Then limit is stirred 400ml dissolved with 130g tetra-(2-methoxyl group-1-Methylethyl) esters of silicon acis
Dichloromethane solution drip 1.5 hours and add in aqueous solution, normal temperature and pressure stirring reaction 2 hours, products therefrom is centrifuged, washes
Wash, be dried.
Then adding gained white solid in Muffle furnace, heating schedule is: first at the uniform velocity rose from room temperature in 1.5 hours
To 200 DEG C；It is then passed through 2 hours, at the uniform velocity rises to 400 DEG C from 200 DEG C；It is then passed through 2 hours, at the uniform velocity rises to 500 from 400 DEG C
℃；It is incubated 6 hours at 500 DEG C；Finally naturally cool to room temperature, i.e. obtain monodisperse silica Nano microsphere.
Being observed as under sweep electron microscope by prepared silica spheres, its scanning electron microscope (SEM) photograph is as it is shown on figure 3, tie
Fruit shows, monodisperse silica sphere particle uniform particle diameter prepared by the present invention, particle diameter is 310nm.
And for example, loading 60ml strong aqua ammonia in a kettle., 2.0g tri-n-octyl methyl ammonium chloride and 50ml water, under normal temperature and pressure
300rpm mechanical agitation 3 hours.Then limit is stirred 600ml dissolved with 300g tetra-(2-methoxyl group-1-Methylethyl) esters of silicon acis
Hexane solution drips 2 hours and adds in aqueous solution, normal temperature and pressure stirring reaction 3 hours, is centrifuged by products therefrom, washs, is dried.
Then adding gained white solid in Muffle furnace, heating schedule is: first at the uniform velocity rose from room temperature in 1.5 hours
To 200 DEG C；It is then passed through 2 hours, at the uniform velocity rises to 400 DEG C from 200 DEG C；It is then passed through 1.5 hours, at the uniform velocity rises to 500 from 400 DEG C
℃；It is incubated 6 hours at 500 DEG C；Finally naturally cool to room temperature, i.e. obtain monodisperse silica Nano microsphere.
Being observed as under sweep electron microscope by prepared silica spheres, its scanning electron microscope (SEM) photograph as shown in Figure 4, is tied
Fruit shows, monodisperse silica sphere particle uniform particle diameter prepared by the present invention, particle diameter is 500nm.
And for example, loading 60ml strong aqua ammonia in a kettle., 2.0g tri-n-octyl methyl ammonium chloride and 50ml water, under normal temperature and pressure
400rpm mechanical agitation 3 hours.Then limit is stirred 650ml dissolved with 380g tetra-(2-methoxyl group-1-Methylethyl) esters of silicon acis
Normal hexane and dichloromethane solution, wherein, normal hexane is 1.5:1 with the mol ratio of dichloromethane, drips and adds to aqueous solution in 2 hours
In, normal temperature and pressure stirring reaction 3 hours, products therefrom is centrifuged, washs, is dried.
Then adding gained white solid in Muffle furnace, heating schedule is: first at the uniform velocity rose from room temperature in 1.5 hours
To 200 DEG C, it is to avoid it is broken that variations in temperature causes silicon ball to occur the soonest；It is then passed through 2 hours, at the uniform velocity rises to 400 DEG C from 200 DEG C；
Then in 1.5 hours, at the uniform velocity rising to 500 DEG C from 400 DEG C, its effect heats up with first paragraph, it is to avoid broken situation occurs in silicon ball；
It is incubated 6 hours at 500 DEG C；Finally naturally cool to room temperature, be washed out, be dried, i.e. obtain monodisperse silica nanometer micro-
Ball.
Being observed as under sweep electron microscope by prepared silica spheres, its scanning electron microscope (SEM) photograph is as it is shown in figure 5, tie
Fruit shows, monodisperse silica sphere particle uniform particle diameter prepared by the present invention, particle diameter is 640nm.
And for example, loading 85ml strong aqua ammonia in a kettle., 3.3g tri-n-octyl methyl ammonium chloride and 80ml water, under normal temperature and pressure
200rpm mechanical agitation 3 hours.Then limit is stirred 700ml dissolved with 450g tetra-(2-methoxyl group-1-Methylethyl) esters of silicon acis
Hexane solution drips 3 hours and adds in aqueous solution, normal temperature and pressure stirring reaction 5 hours, is centrifuged by products therefrom, washs, is dried.
Then adding gained white solid in Muffle furnace, heating schedule is: first at the uniform velocity rose from room temperature in 1.5 hours
To 200 DEG C；It is then passed through 2 hours, at the uniform velocity rises to 400 DEG C from 200 DEG C；It is then passed through 1.5 hours, at the uniform velocity rises to 500 from 400 DEG C
℃；It is incubated 6 hours at 500 DEG C；Finally naturally cool to room temperature, be washed out, be dried, i.e. obtain monodisperse silica nanometer
Microsphere.
By prepared silicon dioxide microsphere as under sweep electron microscope observe, its scanning electron microscope (SEM) photograph as shown in Figure 6,
Result shows, monodisperse silica sphere particle uniform particle diameter prepared by the present invention, and particle diameter is 950nm.
And for example, four (ethoxybutyl) esters of silicon acis being dissolved in 2-methyl heptane, solution concentration is 15%, as described oil
Phase；Then, ammonia and tetrabutylammonium chloride aqueous solution are placed in reactor as described aqueous phase, wherein, ammonia and four fourths
The volume ratio of ammonium chloride aqueous solution is 4:1；The mass fraction of ammonia is 28%, the mass fraction of tetrabutylammonium chloride aqueous solution
It is 5%；Take described aqueous phase 100mL, use mechanical agitation 3 hours under normal temperature and pressure, during stirring, drip described oil phase 400mL, dropping
Stir speed (S.S.) during described oil phase is 220rpm.Afterwards, products therefrom sucking filtration is centrifuged after 5 hours, washs, does by stirring reaction
Dry, it is warming up to 260 DEG C the most again, and is incubated 5.5 hours, be then cooled to room temperature, be centrifuged product collecting, centrifugal basket
Speed is 2200rpm, is then washed by product, is dried, obtains monodisperse silica nanosphere.
And for example, four (methoxy isobutyl base) esters of silicon acis being dissolved in isopentane, solution concentration is 21%, as described oil
Phase；Then, ammonia and tripropyl amyl group aqueous ammonium chloride solution are placed in reactor as described aqueous phase, wherein, ammonia with
The volume ratio of tripropyl amyl group aqueous ammonium chloride solution is 3:1；The mass fraction of ammonia is 27%, tripropyl amyl group ammonium chloride solution
The mass fraction of liquid is 6%；Use mechanical agitation 2 hours under normal temperature and pressure, drip described oil phase 450mL, drip described oil phase
Stir speed (S.S.) is 300rpm.Afterwards, products therefrom sucking filtration is centrifuged after 3.75 hours, washs, is dried by stirring reaction, rises the most again
Temperature is to 260 DEG C, and is incubated 5.5 hours, is then cooled to room temperature, and is centrifuged product collecting, and centrifuge speed is
2500rpm, then washs product, is dried, obtain monodisperse silica nanosphere.
And for example, four (ethyoxyl isobutyl group) esters of silicon acis being dissolved in trichloroethane, solution concentration is 28%, as described oil
Phase；Then, ammonia and triethyl benzyl ammonia chloride aqueous solution are placed in reactor as described aqueous phase, wherein, ammonia with
The volume ratio of triethyl benzyl ammonia chloride aqueous solution is 2:1；The mass fraction of ammonia is 29%, and triethyl benzyl ammonia chloride is water-soluble
The mass fraction of liquid is 3%；Take described aqueous phase 1200mL, use mechanical agitation 2.5 hours under normal temperature and pressure, drip described oil phase
5200mL, the stir speed (S.S.) dripping described oil phase is 360rpm.Afterwards, stirring reaction 4.5 hours after by products therefrom sucking filtration from
The heart, wash, be dried, be warming up to 310 DEG C the most again, and be incubated 7.5 hours, be then cooled to room temperature, product is centrifuged receive
Collection, centrifuge speed is 4000rpm, is then washed by product, is dried, obtains monodisperse silica nanosphere.
And for example, four (ethyoxyl isobutyl group) esters of silicon acis is dissolved in the mixture of trichloroethane and normal butane, as described
Oil phase, wherein, solution concentration is 36%, and trichloroethane is 1:1 with the mol ratio of normal butane；Then, by ammonia and benzyl three fourth
Ammonium chloride aqueous solution is placed in reactor as described aqueous phase, wherein, and ammonia and benzyl tributyl aqueous ammonium chloride solution
Volume ratio is 1:1；The mass fraction of ammonia is 29.8%, and the mass fraction of benzyl tributyl aqueous ammonium chloride solution is 2.6%；Take
Described aqueous phase 2000mL, uses mechanical agitation 3.25 hours under normal temperature and pressure, drips described oil phase 12000mL, it is preferred that can use
Multiple water droppers are simultaneously added dropwise described oil phase, and the stir speed (S.S.) dripping described oil phase is 400rpm.Afterwards, stirring reaction 5.5 hours
After products therefrom sucking filtration be centrifuged, wash, be dried, be warming up to 420 DEG C the most again, and be incubated 7.25 hours, be subsequently cooled to room
Temperature, is centrifuged product collecting, and centrifuge speed is 6500rpm, is then washed by product, is dried, obtains single dispersing dioxy
SiClx nanosphere.
And for example, four (ethyoxyl isobutyl group) esters of silicon acis is dissolved in the mixture of dichloroethanes and pentane, as described
Oil phase, wherein, solution concentration is 45%, and dichloroethanes and pentane are 1:1.5；Then, by ammonia and tetramethyl ammonium chloride water
Solution is placed in reactor as described aqueous phase, and wherein, ammonia is 1:1.5 with the volume ratio of tetramethyl ammonium chloride aqueous solution；
The mass fraction of ammonia is 26.9%, and the mass fraction of tetramethyl ammonium chloride aqueous solution is 1.5%；Take described aqueous phase 250mL, often
Using mechanical agitation 4 hours under normal temperature and pressure, drip described oil phase 2000mL, the stir speed (S.S.) dripping described oil phase is 460rpm.It
After, products therefrom sucking filtration is centrifuged after 5.25 hours, washs, is dried by stirring reaction, is warming up to 480 DEG C the most again, and is incubated 6.5
Hour, it being then cooled to room temperature, be centrifuged product collecting, centrifuge speed is 5500rpm, is then washed by product, does
Dry, obtain monodisperse silica nanosphere.
And for example, four (propoxyl group isopropyl) esters of silicon acis is dissolved in normal octane, as described oil phase, wherein, solution concentration
It is 68%；Then, ammonia and tripropyl amyl group aqueous ammonium chloride solution are placed in reactor as described aqueous phase, wherein, ammonia
Water is 1:2 with the volume ratio of tripropyl amyl group aqueous ammonium chloride solution；The mass fraction of ammonia is 28.1%, tripropyl amyl group chlorination
The mass fraction of aqueous ammonium is 2.3%；Take described aqueous phase 200mL, under normal temperature and pressure, use mechanical agitation 4.25 hours, drip institute
Stating oil phase 1400mL, the stir speed (S.S.) dripping described oil phase is 600rpm.Afterwards, by products therefrom after stirring is reacted 8.5 hours
Sucking filtration is centrifuged, washs, is dried, and is warming up to 580 DEG C the most again, and is incubated 6 hours, is then cooled to room temperature, product is carried out from
The heart is collected, and centrifuge speed is 9500rpm, is then washed by product, is dried, obtains monodisperse silica nanosphere.
And for example, four (ethyoxyl isobutyl group) esters of silicon acis is dissolved in 1,2-dichloropentane, as described oil phase, wherein, molten
Liquid concentration is 57%；Then, ammonia and triethyl benzyl ammonia chloride aqueous solution are placed in reactor as described aqueous phase, its
In, ammonia is 1:3 with the volume ratio of triethyl benzyl ammonia chloride aqueous solution；The mass fraction of ammonia is 27.9%, triethyl group benzyl
The mass fraction of ammonium chloride aqueous solution is 3.5%；Take described aqueous phase 400mL, under normal temperature and pressure, use mechanical agitation 4.25 hours,
Using 5 groups of droppers to drip described oil phase 2000mL altogether, the stir speed (S.S.) dripping described oil phase is 490rpm.Afterwards, stirring reaction 8
After hour, products therefrom sucking filtration is centrifuged, washs, is dried, be warming up to 500 DEG C the most again, and be incubated 9 hours, be subsequently cooled to room
Temperature, is centrifuged product collecting, and centrifuge speed is 7800rpm, is then washed by product, is dried, obtains single dispersing dioxy
SiClx nanosphere.
And for example, four (methoxyl group-2-methylpentane) esters of silicon acis is dissolved in isohexane, as described oil phase, wherein, solution
Concentration is 44%；Then, ammonia and three amyl group ethylmercury chloride aqueous ammoniums are placed in reactor as described aqueous phase, its
In, the volume ratio of ammonia and three amyl group ethylmercury chloride aqueous ammoniums is 1:4；The mass fraction of ammonia is 28%, three amyl group ethyls
The mass fraction of aqueous ammonium chloride solution is 5.3%；Take described aqueous phase 300mL, under normal temperature and pressure, use mechanical agitation 4 hours, use 7
Group dropper drips described oil phase 2100mL altogether, and the stir speed (S.S.) dripping described oil phase is 360rpm.Afterwards, stirring reaction 7 hours
After products therefrom sucking filtration be centrifuged, wash, be dried, be warming up to 350 DEG C the most again, and be incubated 5 hours, be then cooled to room temperature,
Being centrifuged product collecting, centrifuge speed is 7200rpm, is then washed by product, is dried, obtains monodisperse silica
Nanosphere.
Further, embodiments of the invention also include, each technical characteristic of the various embodiments described above, are mutually combined formation
The preparation method of monodisperse silica microspheres.The present invention uses interface method to combine the reaction of liquid liquid interface, phase transfer reaction, urges
Change the process of reaction mechanism synthetic silica Nano microsphere, it is provided that the manufacture new technology of nanometer grade silica, solve
The technique of the seed law of having determined and swelling method is not enough, decreases the production cycle, improves production efficiency, improves nano silicon
Mechanical strength, dispersibility, homogeneity；Low raw-material cost, technological operation simplicity, it is easy to industrializing implementation.
It should be noted that the description of the present invention and accompanying drawing thereof give the preferred embodiment of the present invention, but,
The present invention can be realized by many different forms, however it is not limited to the embodiment described by this specification, these embodiments
Not as the extra restriction to present invention, it is provided that the purpose of these embodiments is to make the understanding to the disclosure
More thorough comprehensive.Further, above-mentioned each technical characteristic continues to be mutually combined, and forms various embodiments the most enumerated above, all
It is considered as the scope that description of the invention is recorded；Further, for those of ordinary skills, can be according to the above description
Improved or converted, and all these modifications and variations all should be belonged to the protection domain of claims of the present invention.
Claims (16)
1. the preparation method of a monodisperse silica microspheres, it is characterised in that employing quaternary ammonium salt is phase transfer catalyst, ammonia
Water is catalyst, and positive esters of silicon acis is silicon source, synthesizes described silicon dioxide microsphere by two phase process；Described phase transfer catalyst is simultaneously
Be present in biphase in；Described quaternary ammonium salt includes alkyl quaternary ammonium salts；Described alkyl quaternary ammonium salts at least includes tetramethyl ammonium chloride, four fourths
Ammonium chloride, tripropyl amyl group ammonium chloride, tri-n-octyl methyl ammonium chloride, triethyl benzyl ammonia chloride, three amyl group ethyl ammonium chlorides
Or benzyl tributyl ammonium chloride one of them.
Preparation method the most according to claim 1, it is characterised in that described phase transfer catalyst dissolubility in biphase is equal
More than one thousandth gram.
Preparation method the most according to claim 2, it is characterised in that described phase transfer catalyst dissolubility in biphase is equal
More than one of percentage gram.
Preparation method the most according to claim 3, it is characterised in that described phase transfer catalyst dissolubility in biphase is equal
More than 10 grams.
Preparation method the most according to claim 1, it is characterised in that described quaternary ammonium salt includes the alkyl that carbon chain lengths is more than 4
Quaternary ammonium salt.
Preparation method the most according to claim 5, it is characterised in that the carbochain total length containing side chain is less than 20 carbon atoms.
Preparation method the most according to claim 1, it is characterised in that described positive esters of silicon acis at least include alkyl or alkoxyl its
One of.
Preparation method the most according to claim 7, it is characterised in that described positive esters of silicon acis is four (alkoxyl-branched alkyls)
Esters of silicon acis.
Preparation method the most according to claim 7, it is characterised in that described positive esters of silicon acis is four (2-methoxyl group-1-methyl second
Base) and/or four (ethoxybutyl) esters of silicon acis.
Preparation method the most according to claim 1, it is characterised in that biphase in described two phase process includes oil phase and aqueous phase,
Wherein, described oil phase includes water-fast organic solvent.
11. preparation methoies according to claim 10, it is characterised in that described oil phase includes alkane, alkyl halide or its mixture.
12. preparation methoies according to claim 10, it is characterised in that described oil phase includes normal hexane or dichloromethane.
13. according to the arbitrary described preparation method of claim 1 to 12, it is characterised in that comprise the following steps:
Step1, is dissolved in the oil phase in described two phase process by described silicon source；
Step2, is placed in reactor as the aqueous phase in described two phase process using described catalyst and described phase transfer catalyst,
Stir and be slowly added described oil phase, for the condensation reaction that is hydrolyzed at water phase and an oil phase interface；
Step3, separates product after stirring reaction.
14. according to preparation method described in claim 13, it is characterised in that
In Step1, four (2-methoxyl group-1-Methylethyl) esters of silicon acis is dissolved in normal hexane, as described oil phase；
In Step2, ammonia and tri-n-octyl methyl ammonium chloride aqueous solution are placed in reactor as described aqueous phase, stir and drip
Add described oil phase；
In Step3, products therefrom sucking filtration is centrifuged, washs after 2 to 10 hours, is dried by stirring reaction, then heat to 200 DEG C-
600 DEG C, and it is incubated 5-10 hour, it is then cooled to room temperature, carries out product washing, being dried, obtain monodisperse silica and receive
Rice ball.
15. according to preparation method described in claim 14, it is characterised in that
Load ammonia and tri-n-octyl methyl ammonium chloride aqueous solution, wherein, ammonia and tri-n-octyl methyl ammonium chloride water in a kettle.
The volume ratio of solution is 4:1 to 1:4, and the mass fraction of ammonia is 26%-30%, the quality of tri-n-octyl methyl ammonium chloride aqueous solution
Mark is 1%～6%.
16. according to preparation method described in claim 14, it is characterised in that
In Step1, four (2-methoxyl group-1-Methylethyl) esters of silicon acis being dissolved in normal hexane, solution concentration is 5%～80%,
As described oil phase；
In Step2, ammonia and tri-n-octyl methyl ammonium chloride aqueous solution are placed in reactor as described aqueous phase, normal temperature and pressure
Lower mechanical agitation 1-5 hour, drips described oil phase, and its volume is 2 to 9 times of described aqueous phase volume, drips described oil phase
Stir speed (S.S.) is 200rpm-600rpm；
In Step3, products therefrom sucking filtration is centrifuged after 2 to 10 hours, washs, is dried by stirring reaction, then rises in Muffle furnace
Temperature is to 200 DEG C-600 DEG C, and is incubated 5-10 hour, is then cooled to room temperature, and is centrifuged product collecting, and centrifuge speed is
2000rpm～10000rpm, then washs product, is dried, obtain monodisperse silica nanosphere.
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