CN100391840C - Reactive nanometer particle of silica dioxide - Google Patents
Reactive nanometer particle of silica dioxide Download PDFInfo
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- CN100391840C CN100391840C CNB2004100101259A CN200410010125A CN100391840C CN 100391840 C CN100391840 C CN 100391840C CN B2004100101259 A CNB2004100101259 A CN B2004100101259A CN 200410010125 A CN200410010125 A CN 200410010125A CN 100391840 C CN100391840 C CN 100391840C
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000002245 particle Substances 0.000 title abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 78
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 78
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 74
- -1 silicate ester Chemical class 0.000 claims abstract description 55
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 39
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000413 hydrolysate Substances 0.000 claims abstract description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000002105 nanoparticle Substances 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 235000019353 potassium silicate Nutrition 0.000 claims description 11
- 235000019270 ammonium chloride Nutrition 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 125000003700 epoxy group Chemical group 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 239000006166 lysate Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- 238000006053 organic reaction Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract 2
- 239000004115 Sodium Silicate Substances 0.000 abstract 1
- 229910052911 sodium silicate Inorganic materials 0.000 abstract 1
- 229960004756 ethanol Drugs 0.000 description 21
- 239000012153 distilled water Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 230000003292 diminished effect Effects 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229940022682 acetone Drugs 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- HBZPRQCNASJKHW-UHFFFAOYSA-N trimethoxysilyl prop-2-enoate Chemical compound CO[Si](OC)(OC)OC(=O)C=C HBZPRQCNASJKHW-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
- Silicon Compounds (AREA)
Abstract
The present invention discloses a reactive silica nanometer particle. The surface of the silica nanometer particle is bonded to reactive organic compounds containing silicon, which account for 5 to 80 wt% of the silica nanometer particle. The reactive silica nanometer particle can be prepared in a way that the reactive organic compounds containing silicon react with silicate ester under the condition that organic media exist, and then, the reaction product is hydrolyzed under the condition that the pH value is from 8 to 11; or silicate ester is hydrolyzed in organic media under the condition that the pH value is from 8 to 11, and then, the hydrolysate product reacts with the reactive organic compounds containing silicon; or sodium silicate is hydrolyzed in a mixed medium of alcohol(C2 to C12) and water under the condition that the pH value is from 8 to 11, and then, the hydrolysate product reacts with the reactive organic compounds containing silicon in organic media. The nanometer particle has good dispersivity in organic media and can be used as one of components to participate in organic reactions and polymerizations.
Description
Technical field
The invention belongs to technical field of nano material, particularly a kind of reacting nano silicon dioxide microparticle and preparation method thereof.
Background technology
The character of high polymer nano matrix material depends on the selection design of nano material and the INTERFACE DESIGN of matrix material.The center of the synthetic design of nano composite material is exactly the granularity and the degree of scatter of nano material, with the synergistic effect of two kinds of components farthest bringing into play different attribute.Organic polymer in the most polymers inorganic nano material with inorganic alternate be to combine with weak interaction such as hydrogen bond, Van der Waals force, hydrophilic-hydrophobic balance etc.If organic polymer is connected with stronger chemical bond mutually with inorganic, then can avoid taking place macroface to a great extent and separate, the gained material also can improve a lot on performance.
Summary of the invention
The object of the present invention is to provide a kind of reactive silicon dioxide nanoparticle and preparation method thereof, this nanoparticle has good dispersion in organic medium, can be used as one of component and participates in organic reaction or polyreaction.
For reaching above-mentioned purpose, the present invention adopts following technical scheme: the reactive silicon dioxide nanoparticle, the silica nanoparticles surface bond has the silicon-containing organic compound with reactive behavior, and silicon-containing organic compound shared weight percent in silica nanoparticles is 5-80%.
Silicon-containing organic compound shared weight percent in silica nanoparticles is 10-60%.
Silicon-containing organic compound is R ' mSi (OR ") n and a derivative thereof; R " C chain length CR "=1-18; C chain length CR '=1-20 of R '; 1≤n≤3; 1≤m≤3; R ' m has active function groups, active function groups are hydroxyl, carboxyl, two key, epoxy group(ing), amino, sulfydryl, urea groups, four sulfenyls or halogen.
The preparation method of reactive silicon dioxide nanoparticle comprises that silicon-containing organic compound and silicon ester with reactive behavior desolventize at reactions steps, reaction product hydrolysing step, hydrolysate under P H=8-11 condition in the presence of the organic medium, drying step; Wherein, the mol ratio of 30-80 ℃ of silicon-containing organic compound and silicon ester temperature of reaction, reaction times 1-5 hour, silicon-containing organic compound and silicon ester is 1: 0.1-10,30-80 ℃ of reaction product hydrolysis temperature of reaction, reaction times 1-30 hour, the concentration of silicon ester in organic medium is (0.1-3) * 10
-3Mol/l.
Silicon-containing organic compound is R ' mSi (OR ") n; R " C chain length CR "=1-18; C chain length CR '=1-20 of R '; 1≤n≤3; 1≤m≤3, R ' m has active function groups, active function groups is hydroxyl, carboxyl, two key, epoxy group(ing), amino, sulfydryl, urea groups, four sulfenyls or halogen; silicon ester is the positive silicon ester of C1-C18, organic medium is a kind of of tetrahydrofuran (THF), ethanol, acetone, toluene, dimethylbenzene, phthalic ester or more than one combination.
Silicon ester is the positive silicon ester of C1-C6, and the mol ratio of silicon-containing organic compound and silicon ester is 1: 0.5-8, organic medium are that the volume ratio of ethanol or ethanol and acetone is 0.5-5: 1 mixing solutions; The hydrolysis reaction pH value is with ammoniacal liquor or aqueous ammonium chloride solution adjustment.
The preparation method of reactive silicon dioxide nanoparticle, comprise silicon ester under the PH=8-11 condition in organic medium hydrolysing step, hydrolysate and have that the silicon-containing organic compound reactions steps of reactive behavior, above-mentioned reaction product desolventize, drying step; Wherein, hydrolysising reacting temperature 30-80 ℃, reaction times 1-30 hour, the concentration of silicon ester in organic medium are (0.1-3) * 10
-3Mol/l, the mol ratio of 30-80 ℃ of hydrolysate and silicon-containing organic compound temperature of reaction, reaction times 1-5 hour, silicon-containing organic compound and silicon ester is 1: 0.1-10.
Silicon-containing organic compound is R ' mSi (OR ") n; R " C chain length CR "=1-18; C chain length CR '=1-20 of R '; 1≤n≤3; 1≤m≤3, R ' m has active function groups, active function groups is hydroxyl, carboxyl, two key, epoxy group(ing), amino, sulfydryl, urea groups, four sulfenyls or halogen; silicon ester is the positive silicon ester of C1-C18, organic medium is a kind of of tetrahydrofuran (THF), ethanol, acetone, toluene, dimethylbenzene, phthalic ester or more than one combination.
Silicon ester is the positive silicon ester of C1-C6, and the hydrolysis reaction pH value is with ammoniacal liquor or aqueous ammonium chloride solution adjustment; The mol ratio of silicon-containing organic compound and silicon ester is 1: 0.5-8, organic medium are that the volume ratio of ethanol or ethanol and acetone is 0.5-5: 1 mixing solutions.
The preparation method of reactive silicon dioxide nanoparticle, comprise water glass under the PH8-11 condition in the blending agent of the alcohol of C2-C12 and water hydrolysing step, hydrolysate and silicon-containing organic compound reactions steps, reaction product in organic medium with reactive behavior desolventizes, drying step; Wherein, 30-100 ℃ of water glass hydrolysising reacting temperature, reaction times 1-5 hour, the concentration of water glass is 0.01-0.12mol/l, and hydrolysate and 30-80 ℃ of silicon-containing organic compound reactions steps temperature of reaction, reaction times 1-15 hour, silicon-containing organic compound and water glass mol ratio are 1: 0.1-10.
Silicon-containing organic compound is R ' m Si (OR ") n; R " C chain length CR "=1-18; C chain length CR '=1-20 of R '; 1≤n≤3; 1≤m≤3, R ' m has active function groups, active function groups is hydroxyl, carboxyl, two key, epoxy group(ing), amino, sulfydryl, urea groups, four sulfenyls or halogen; silicon ester is the positive silicon ester of C1-C18, organic medium is a kind of of tetrahydrofuran (THF), ethanol, acetone, toluene, dimethylbenzene, phthalic ester or more than one combination.
The hydrolysis reaction pH value is 1 with ammoniacal liquor or aqueous ammonium chloride solution adjustment, silicon-containing organic compound and water glass mol ratio: 0.5-8, organic medium are that the volume ratio of ethanol or ethanol and acetone is 0.5-5: 1 mixing solutions.
Among the present invention, silicon-containing organic compound in the silica nanoparticles surface, forms stable chemically modified layer with chemical bonding.The not only size of may command nanoparticle and the generation of reunion of this modification, make nanoparticle can stable dispersion in organic medium, the more important thing is that it has good reactive behavior, can be used as raw material and participate in organic reaction or high molecular polymerization.When participating in polyreaction as raw material, can in polymkeric substance, introduce the silica nanoparticles that combines with chemical bond, be used for the preparation of polymer novel materials such as rubber, plastics, fiber, tackiness agent, functional paint and protective material or enhancing, wear preventive additive and other property-modifying additive of polymer materials: the functional additive that is used as macromolecular materials such as leather function finishing agent, fiber functional modifier: as the antiwear and friction-reducing additive of lubricating oil, hypotonic oil well extender etc.Regular with silicon ester synthetic nanoparticle particle, and monodispersity is good.Be irregularly shaped with water glass synthetic nanoparticle, but reaction conditions is easy to control, manufacturing process is comparatively easy, is easy to industrialization, and cost is lower.
Embodiment
Embodiment 1, take by weighing the Na of 0.05mol
2SiO
39H2O puts into the 250ml three-necked bottle, adds the dissolving of 150ml distilled water and alcoholic acid mixing solutions (distilled water and ethanol volume ratio are 2: 1), under agitation drips ammonium chloride solution, and pH value is reached about 10.Be warming up to 80 ℃, insulation reaction 3 hours.Decompress filter is used distilled water wash 2 times.Filtration under diminished pressure removes most of moisture then.Filter cake is transferred to three-necked bottle, adds the 150ml dehydrated alcohol, add 0.0125mol KH-550 (γ-An Bingjisanyiyangjiguiwan), reacted 5 hours down at 60 ℃.Gained solution is carried out spraying drying, get white powder.Be the reactive SiO of RNS-Am type oil-dispersing property
2Nano powder.
Embodiment 2, take by weighing the Na of 0.1mol
2SiO
39H
2O puts into the 250ml three-necked bottle, adds the dissolving of 150ml distilled water and alcoholic acid mixing solutions (distilled water and ethanol volume ratio are 2: 1), under agitation drips ammonium chloride solution, and pH value is reached about 10.Be warming up to 80 ℃, insulation reaction 3 hours.Decompress filter is used distilled water wash 2 times.Filtration under diminished pressure removes most of moisture then.Filter cake is transferred to three-necked bottle, adds the mixing solutions (ethanol and acetone volume ratio are 1.5: 1) of 150ml dehydrated alcohol and acetone, add 0.01mol KH-570 (propyl group acryloxy Trimethoxy silane), reacted 2 hours down at 30 ℃.The isocaprylic acid that adds 0.01mmol then reacted 2 hours down at 80 ℃.Gained solution is carried out spraying drying, get white powder.Be the reactive SiO of RNS-D type oil-dispersing property
2Nano powder.
Embodiment 3, take by weighing the Na of 0.05mol
2SiO
35H
2O puts into the 250ml three-necked bottle, adds the dissolving of 150ml distilled water and alcoholic acid mixing solutions (distilled water and ethanol volume ratio are 2: 1), under agitation drips ammonium chloride solution, and pH value is reached about 10.Be warming up to 80 ℃, insulation reaction 3 hours.Decompress filter is used distilled water wash 2 times.Filtration under diminished pressure removes most of moisture then.Filter cake is transferred to three-necked bottle, the mixing solutions (ethanol and acetone volume ratio are 1.5: 1) that adds 150ml dehydrated alcohol and acetone, reacted 2 hours down at 40 ℃, drip 0.01molKH-590 (γ-Qiu Jibingjisanjiayangjiguiwan) then, isothermal reaction 2 hours, after filtration, drying, promptly get the reactive SiO of RNS-Q type oil-dispersing property
2Nanoparticle.
Embodiment 4, take by weighing the Na of 0.1mol
2SiO
39H
2O puts into the 250ml three-necked bottle, adds the dissolving of 150ml distilled water and alcoholic acid mixing solutions (distilled water and ethanol volume ratio are 2: 1), under agitation drips ammonium chloride solution, and pH value is reached about 10.Be warming up to 80 ℃, insulation reaction 3 hours.Decompress filter is used distilled water wash 2 times.Filtration under diminished pressure removes most of moisture then.Filter cake is transferred to three-necked bottle, add in the mixing solutions of the 50ml ethanol of 30 ℃ of constant temperature and 100ml acetone, add 0.02molKH-560 (γ-glycidyl ether propyl trimethoxy silicane) isothermal reaction 4 hours then, after solvent is volatilized, obtain containing the reactive SiO of oil-dispersing property of epoxy group(ing)
2Nanoparticle.
Embodiment 5,20ml dehydrated alcohol and 40mmol tetraethoxy are added in the three-necked flask, be warming up to 60 ℃, add 40mmolKH-550 (γ-An Bingjisanyiyangjiguiwan) and 20ml alcoholic acid mixing solutions, isothermal reaction 2 hours, drip then and contain the ammoniacal liquor of 2ml weight percent concentration 28% and the 10ml ethanolic soln of 1.3ml water, the adularescent gelatinous precipitate occurs gradually, continue isothermal reaction 2 hours, most solutions is removed in underpressure distillation, drying obtains containing the amino reactive SiO with the γ-An Bingjisanyiyangjiguiwan modification
2Nanoparticle.
Embodiment 6, the 100mmol tetraethoxy is slowly splashed in the mixing solutions (volume ratio of ethanol and acetone is 1.5: 1) of the 100ml ethanol of the ammoniacal liquor that contains 4ml weight percent concentration 25% of 30 ℃ of constant temperature and 3.7ml water and acetone, isothermal reaction 5 hours, drip 100mlKH-590 (γ-Qiu Jibingjisanjiayangjiguiwan) then, isothermal reaction 2 hours, after filtration, drying, promptly get the SiO that modifies with γ-mercaptopropyl trimethoxysilane that contains sulfydryl
2Nanoparticle.
Embodiment 7,80mmol tetraethoxy, 20mmolKH-560 (γ-glycidyl ether propyl trimethoxy silicane) are added in the mixing solutions (volume ratio of ethanol and acetone is 1: 2) of the 100ml ethanol of 30 ℃ of constant temperature and acetone, isothermal reaction 2 hours, splash into the 100ml ethanolic soln of the ammoniacal liquor that contains 3.3ml weight percent concentration 25% then, isothermal reaction 4 hours, after solvent is volatilized, obtain containing the reactive SiO with the KH-560 modification of epoxy group(ing)
2Nanoparticle.
Embodiment 8,50ml dehydrated alcohol and 25ml methyl silicate are added in the three-necked flask, slowly splash into the mixing solutions of the ammoniacal liquor of 50ml ethanol and 10ml weight percent concentration 25% then, stirred at normal temperatures 1 hour; Add 20ml and contain the ethanolic soln of 0.5mmolA-143 (γ-r-chloropropyl trimethoxyl silane), reflux 4 hours, underpressure distillation removes and desolvates then, dry powder, be the chloride SiO that modifies with γ-r-chloropropyl trimethoxyl silane
2Nanoparticle.
Claims (9)
1. the preparation method of reactive silicon dioxide nanoparticle, it is characterized in that, comprise that silicon-containing organic compound and silicon ester with reactive behavior desolventize at reactions steps, reaction product hydrolysing step, hydrolysate under the PH=8-11 condition in the presence of the organic medium, drying step; Wherein, the mol ratio of 30-80 ℃ of silicon-containing organic compound and silicon ester temperature of reaction, reaction times 1-5 hour, silicon-containing organic compound and silicon ester is 1: 0.1-10,30-80 ℃ of reaction product hydrolysis temperature of reaction, reaction times 1-30 hour, the concentration of silicon ester in organic medium is (0.1-3) * 10
-3Mol/l.
2. preparation method as claimed in claim 1, it is characterized in that, silicon-containing organic compound is R ' mSi (OR ") n; R " C chain length CR "=1-18; C chain length CR '=1-20 of R '; 1≤n≤3; 1≤m≤3; R ' m has active function groups; active function groups is hydroxyl, carboxyl, two key, epoxy group(ing), amino, sulfydryl, urea groups, four sulfenyls or halogen, silicon ester is the positive silicon ester of C1-C18, and organic medium is a kind of of tetrahydrofuran (THF), ethanol, acetone, toluene, dimethylbenzene, phthalic ester or more than one combination.
3. method as claimed in claim 1 or 2 is characterized in that, silicon ester is the positive silicon ester of C1-C6, and the mol ratio of silicon-containing organic compound and silicon ester is 1: 0.5-8, organic medium are that the volume ratio of ethanol or ethanol and acetone is 0.5-5: 1 mixing solutions; The hydrolysis reaction pH value is with ammoniacal liquor or aqueous ammonium chloride solution adjustment.
4. the preparation method of reactive silicon dioxide nanoparticle, it is characterized in that, comprise silicon ester under the PH=8-11 condition in organic medium hydrolysing step, hydrolysate and have that the silicon-containing organic compound reactions steps of reactive behavior, above-mentioned reaction product desolventize, drying step; Wherein, hydrolysising reacting temperature 30-80 ℃, reaction times 1-30 hour, the concentration of silicon ester in organic medium are (0.1-3) * 10
-3Mol/l, the mol ratio of 30-80 ℃ of hydrolysate and silicon-containing organic compound temperature of reaction, reaction times 1-5 hour, silicon-containing organic compound and silicon ester is 1: 0.1-10.
5. method as claimed in claim 4, it is characterized in that, silicon-containing organic compound is R ' mSi (OR ") n; R " C chain length CR "=1-18; C chain length CR '=1-20 of R '; 1≤n≤3; 1≤m≤3; R ' m has active function groups; active function groups is hydroxyl, carboxyl, two key, epoxy group(ing), amino, sulfydryl, urea groups, four sulfenyls or halogen, silicon ester is the positive silicon ester of C1-C18, and organic medium is a kind of of tetrahydrofuran (THF), ethanol, acetone, toluene, dimethylbenzene, phthalic ester or more than one combination.
6. as claim 4 or 5 described methods, it is characterized in that silicon ester is the positive silicon ester of C1-C6, the hydrolysis reaction pH value is with ammoniacal liquor or aqueous ammonium chloride solution adjustment; The mol ratio of silicon-containing organic compound and silicon ester is 1: 0.5-8, organic medium are that the volume ratio of ethanol or ethanol and acetone is 0.5-5: 1 mixing solutions.
7. the preparation method of reactive silicon dioxide nanoparticle, it is characterized in that, comprise water glass under the PH8-11 condition in the blending agent of the alcohol of C2-C12 and water hydrolysing step, hydrolysate and silicon-containing organic compound reactions steps, reaction product in organic medium with reactive behavior desolventizes, drying step; Wherein, 30-100 ℃ of water glass hydrolysising reacting temperature, reaction times 1-5 hour, the concentration of water glass is 0.01-0.12mol/l, and hydrolysate and 30-80 ℃ of silicon-containing organic compound reactions steps temperature of reaction, reaction times 1-15 hour, silicon-containing organic compound and water glass mol ratio are 1: 0.1-10.
8. preparation method as claimed in claim 7, it is characterized in that, silicon-containing organic compound is R ' mSi (OR ") n; R " C chain length CR "=1-18; C chain length CR '=1-20 of R '; 1≤n≤3; 1≤m≤3; R ' m has active function groups; active function groups is hydroxyl, carboxyl, two key, epoxy group(ing), amino, sulfydryl, urea groups, four sulfenyls or halogen, silicon ester is the positive silicon ester of C1-C18, and organic medium is a kind of of tetrahydrofuran (THF), ethanol, acetone, toluene, dimethylbenzene, phthalic ester or more than one combination.
9. as claim 7 or 8 described preparation methods, it is characterized in that, the hydrolysis reaction pH value is 1 with ammoniacal liquor or aqueous ammonium chloride solution adjustment, silicon-containing organic compound and water glass mol ratio: 0.5-8, organic medium are that the volume ratio of ethanol or ethanol and acetone is 0.5-5: 1 mixing solutions.
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|---|---|---|---|
| CNB2004100101259A CN100391840C (en) | 2004-03-12 | 2004-03-12 | Reactive nanometer particle of silica dioxide |
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|---|---|---|---|
| CNB2004100101259A CN100391840C (en) | 2004-03-12 | 2004-03-12 | Reactive nanometer particle of silica dioxide |
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| CN100391840C true CN100391840C (en) | 2008-06-04 |
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| CN103146329A (en) * | 2011-12-07 | 2013-06-12 | 南京工程学院 | Preparation method for epoxy adhesive modified by surface-modified nanoparticles |
| CN103450727B (en) * | 2013-09-20 | 2016-03-23 | 云南银峰新材料有限公司 | A kind of preparation method containing the super two thin coating of fluorocarbon chain nanometer |
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| CN107140650B (en) * | 2017-04-07 | 2021-04-20 | 河南大学 | Silicon dioxide nano surfactant and preparation method thereof |
| CN111019198B (en) * | 2019-12-26 | 2021-01-26 | 河南大学 | Natural rubber/nano silicon dioxide composite material and preparation method thereof |
| CN112226221B (en) * | 2020-10-19 | 2022-03-01 | 河南大学 | Nano silicon dioxide oil displacement agent and preparation method and application thereof |
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| US3953487A (en) * | 1973-09-03 | 1976-04-27 | Elektroschmelzwerk Kempten Gmbh | Process for preparing hydrophobic silicon dioxide |
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| US6174926B1 (en) * | 1999-01-13 | 2001-01-16 | Cabot Corporation | Method of preparing organically modified silica |
| CN1280993A (en) * | 1999-07-20 | 2001-01-24 | 四川大学 | Ultrasonic radiation process for preparing composite-material of polymer and nm-class inorganic particles |
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| US3953487A (en) * | 1973-09-03 | 1976-04-27 | Elektroschmelzwerk Kempten Gmbh | Process for preparing hydrophobic silicon dioxide |
| US4017528A (en) * | 1973-11-16 | 1977-04-12 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Preparation of organically modified silicon dioxides |
| CN1183379A (en) * | 1997-12-30 | 1998-06-03 | 中国科学院感光化学研究所 | Process for preparing nm silicon dioxide granule from alkali metal silicate |
| US6174926B1 (en) * | 1999-01-13 | 2001-01-16 | Cabot Corporation | Method of preparing organically modified silica |
| CN1280993A (en) * | 1999-07-20 | 2001-01-24 | 四川大学 | Ultrasonic radiation process for preparing composite-material of polymer and nm-class inorganic particles |
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