CN100341781C - Reactive nanometer particle of silica dioxide - Google Patents
Reactive nanometer particle of silica dioxide Download PDFInfo
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- CN100341781C CN100341781C CNB2004100101244A CN200410010124A CN100341781C CN 100341781 C CN100341781 C CN 100341781C CN B2004100101244 A CNB2004100101244 A CN B2004100101244A CN 200410010124 A CN200410010124 A CN 200410010124A CN 100341781 C CN100341781 C CN 100341781C
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- Prior art keywords
- organic acid
- reaction
- silicon ester
- ethanol
- ester
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000002245 particle Substances 0.000 title abstract description 14
- 150000007524 organic acids Chemical class 0.000 claims abstract description 41
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 15
- 239000000413 hydrolysate Substances 0.000 claims abstract description 14
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 51
- -1 silicon ester Chemical class 0.000 claims description 51
- 229910052710 silicon Inorganic materials 0.000 claims description 40
- 239000010703 silicon Substances 0.000 claims description 40
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 239000002105 nanoparticle Substances 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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
- 235000019353 potassium silicate Nutrition 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 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
- 238000000034 method Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 239000006166 lysate Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 238000006053 organic reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 235000005985 organic acids Nutrition 0.000 abstract 4
- 239000003513 alkali Substances 0.000 abstract 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract 2
- 239000000047 product Substances 0.000 abstract 2
- 239000004115 Sodium Silicate Substances 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 229910052911 sodium silicate Inorganic materials 0.000 abstract 1
- 229960004756 ethanol Drugs 0.000 description 12
- 239000002253 acid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229940022682 acetone Drugs 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 230000003292 diminished effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 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
- 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
- 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
- 238000001556 precipitation Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Abstract
The present invention discloses a reactive nanometer particle of silica dioxide, which belongs to the technical field of nanometer materials. The surface of the nanometer particle of silicon dioxide is bonded to reactive organic acids which account for 5 to 80 wt% of the nanometer particle of silicon dioxide. The nanometer particle of silicon dioxide can be prepared in the way that the reactive organic acids and silicate react each other in organic media, and then the reaction product is hydrolyzed under alkali conditions. The nanometer particle of silicon dioxide can also be prepared in the way that silicate is hydrolyzed under alkali conditions, and then the hydrolysate product reacts with the reactive organic acids. The nanometer particle of silicon dioxide can also be prepared in the way that sodium silicate is hydrolyzed under alkali conditions, and then, the hydrolysate product reacts with the reactive organic acids. The nanometer particle has good dispersivity in organic media and has reactivity simultaneously; therefore, the nanometer particle can be used as raw materials to participate in organic reactions or 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 polymer inorganic nano composite material not only has character such as the surface effects, quantum size effect of nano material, and rigidity, dimensional stability and the thermostability of inorganics and toughness, processibility and the dielectric properties of polymkeric substance blent into one, thereby produce many special performances.Show wide application prospect in fields such as electronics, optics, mechanics, biology.For the matrix material that obtains to have good stability, nanoparticle is fixed in the polymeric substrate firmly, prevent that nanoparticle from assembling and produce and be separated.Existing polymer inorganic nano composite material is many with weak Intermolecular Forces such as hydrogen bond, Van der Waals force or utilize the long-chain iris action of polymkeric substance that nanoparticle is evenly distributed in the polymeric matrix.These methods have limited the usage quantity of nanoparticle in matrix material, and the stability of matrix material can not be guaranteed fully.
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 participate in organic reaction or polyreaction, make the inorganic nano-particle stable dispersion in polymkeric substance.
For reaching above-mentioned purpose, the present invention adopts following technical scheme: a kind of reactive silicon dioxide nanoparticle, the silica nanoparticles surface bond has the organic acid with reactive behavior, and organic acid shared weight percent in silica nanoparticles is 5-80%.
Organic acid shared weight percent in silica nanoparticles is 10-60%.
Organic acid is RCOOH, and the carbon chain lengths of R is C2-C20, has carboxyl, hydroxyl, two key, epoxy group(ing), amino, sulfydryl or halogen on the R.
A kind of preparation method of reactive silicon dioxide nanoparticle, comprise that organic acid 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, have
The mol ratio of machine acid and 30-80 ℃ of silicon ester temperature of reaction, reaction times 2-8 hour, organic acid and silicon ester is 1: 0.1-10,30-80 ℃ of reaction product hydrolysis temperature of reaction, reaction times 2-15 hour, the concentration of silicon ester in organic medium is (0.1-3) * 10
-3Mol/l.
Organic acid is RCOOH, the carbon chain lengths of R is C2-C20, have carboxyl, hydroxyl, two key, epoxy group(ing), amino, sulfydryl or halogen on the R, 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.
Silicon ester is the positive silicon ester of C1-C6, and the mol ratio of organic acid 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.
A kind of 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 organic acid reaction step of reactive behavior, above-mentioned reaction product desolventize, drying step; Wherein, silicon ester hydrolysising reacting temperature 30-80 ℃, reaction times 2-8 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 organic acid reaction temperature, reaction times 2-15 hour, organic acid and silicon ester is 1: 0.1-10.
Organic acid is RCOOH, the carbon chain lengths of R is C2-C20, have carboxyl, hydroxyl, two key, epoxy group(ing), amino, sulfydryl or halogen on the R, 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.
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 organic acid 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.
A kind of 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 organic acid 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 30-100 ℃ of organic acid reaction step reaction temperature, reaction times 2-15 hour, organic acid and water glass mol ratio are 1: 0.1-10.
Organic acid is RCOOH, the carbon chain lengths of R is C2-C20, have carboxyl, hydroxyl, two key, epoxy group(ing), amino, sulfydryl or halogen on the R, 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 that the volume ratio of ethanol or ethanol and acetone is 0.5-5 with ammoniacal liquor or aqueous ammonium chloride solution adjustment, the organic medium of hydrolysate and organic acid reaction: 1 mixing solutions, organic acid and water glass mol ratio are 1: 0.5-8.
Among the present invention, organic acid 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 makes the nanoparticle stable dispersion in organic medium, the more important thing is that it has good reactive behavior, can be used as raw material and participates 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; Functional additive as macromolecular materials such as leather function finishing agent, fiber functional modifiers: 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, and organic acid is in conjunction with comparatively firm.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 1,20ml dehydrated alcohol and 40mmol tetraethoxy are added in the three-necked flask, be warming up to 60 ℃, add methacrylic acid 40mmol, isocaprylic acid 40mmol and 20ml alcoholic acid mixing solutions, constant temperature refluxed 2 hours for 60 ℃, drip then and contain the ammoniacal liquor of 2ml weight percent concentration 25% and the 10ml ethanolic soln of 1.3ml water, continue 60 ℃ of reactions of constant temperature 5 hours.Spraying drying obtains the white powder material then, promptly contains the reacting nano particulate with methacrylic acid and isocaprylic acid modification of two keys, and particle diameter is 10-20nm.
Embodiment 2, the 40mmol tetraethoxy is added in the mixing solutions of the 30ml ethanol of 60 ℃ of constant temperature and 20ml acetone, the isocaprylic acid and the 20ml alcoholic acid mixing solutions that add 40mmol hexanodioic acid and 40mmol then, 60 ℃ of reactions of constant temperature 2 hours, dropping contains the ammoniacal liquor of 2ml weight percent concentration 25% and the 10ml ethanolic soln of 1.3ml water then, reacts 5 hours.Adularescent precipitation generates, after filtration, drying, promptly obtain containing carboxyl with hexanodioic acid and
The reactive oxidants silicon nanometer particle that isocaprylic acid is modified.
Embodiment 3, the 40mmol tetraethoxy is added in the 20ml ethanolic soln of 60 ℃ of constant temperature, drip the 20ml ethanolic soln that contains 40mmol lactic acid, isothermal reaction 3 hours.Splash into the 10ml ethanolic soln of the ammoniacal liquor that contains 1.7ml weight percent concentration 28% then, isothermal reaction 4 hours.After the solvent evaporates, drying obtains containing the reactable monox nanometer particulate of hydroxyl.
Embodiment 4, take by weighing the Na of 0.05mol
2SiO
35H
2O puts into the 250ml three-necked bottle, adds 150ml distilled water and alcoholic acid mixing solutions (distilled water and ethanol volume ratio are 2: 1, down together) dissolving, under agitation drips ammonium chloride solution, and pH value is reached about 11.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 of 100ml ethanol and 50ml acetone.Add 0.01mol methacrylic acid and 0.01mol isocaprylic acid then, isothermal reaction 4 hours.After the solvent evaporates, drying obtains containing the oil-dispersing property reactive oxidants silicon nanometer particle of two keys.
Embodiment 5, take by weighing the Na of 0.1mol
2SiO
35H
2O puts into the 250ml three-necked bottle, adds the dissolving of 150ml distilled water and alcoholic acid mixing solutions, under agitation drips ammonium chloride solution, and pH value is reached about 11.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 ethanolic soln, mixing.Add 0.02mol lactic acid then, 80 ℃ of reactions 4 hours, underpressure distillation removes and to desolvate then, dry powder, be the oil-dispersing property reactive oxidants silicon nanometer particle of hydroxyl.
Claims (9)
1, a kind of preparation method of reactive silicon dioxide nanoparticle, it is characterized in that, comprise that organic acid 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 organic acid and silicon ester temperature of reaction, reaction times 2-8 hour, organic acid and silicon ester is 1: 0.1-10,30-80 ℃ of reaction product hydrolysis temperature of reaction, reaction times 2-15 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, organic acid is RCOOH, the carbon chain lengths of R is C2-C20, have carboxyl, hydroxyl, two key, epoxy group(ing), amino, sulfydryl or halogen on the R, 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 organic acid 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; Hydrolysis reaction pH value is with ammoniacal liquor or aqueous ammonium chloride solution adjustment.
4, a kind of 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 organic acid reaction step of reactive behavior, above-mentioned reaction product desolventize, drying step; Wherein, silicon ester hydrolysising reacting temperature 30-80 ℃, reaction times 2-8 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 organic acid reaction temperature, reaction times 2-15 hour, organic acid and silicon ester is 1: 0.1-10.
5, preparation method as claimed in claim 4, it is characterized in that, organic acid is RCOOH, the carbon chain lengths of R is C2-C20, have carboxyl, hydroxyl, two key, epoxy group(ing), amino, sulfydryl or halogen on the R, 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.
As claim 4 or 5 described methods, it is characterized in that 6, silicon ester is the positive silicon ester of C1-C6, hydrolysis reaction pH value is with ammoniacal liquor or aqueous ammonium chloride solution adjustment; The mol ratio of organic acid 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, a kind of 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 organic acid 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 30-100 ℃ of organic acid reaction step reaction temperature, reaction times 2-15 hour, organic acid and water glass mol ratio are 1: 0.1-10.
8, preparation method as claimed in claim 7, it is characterized in that, organic acid is RCOOH, the carbon chain lengths of R is C2-C20, have carboxyl, hydroxyl, two key, epoxy group(ing), amino, sulfydryl or halogen on the R, 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, hydrolysis reaction pH value is with ammoniacal liquor or aqueous ammonium chloride solution adjustment, the organic medium of hydrolysate and organic acid reaction is that the volume ratio of ethanol or ethanol and acetone is 0.5-5: 1 mixing solutions, organic acid and water glass mol ratio are 1: 0.5-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100101244A CN100341781C (en) | 2004-03-12 | 2004-03-12 | Reactive nanometer particle of silica dioxide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100101244A CN100341781C (en) | 2004-03-12 | 2004-03-12 | Reactive nanometer particle of silica dioxide |
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| CN1666953A CN1666953A (en) | 2005-09-14 |
| CN100341781C true CN100341781C (en) | 2007-10-10 |
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| CN102617805A (en) * | 2012-03-23 | 2012-08-01 | 河南大学 | Method for modifying unsaturated polyester resin by in-situ polymerization of reactive nano-SiO2 |
| CN103289031B (en) * | 2013-06-09 | 2015-06-10 | 河南大学 | High-transparency super-hydrophobicity coating material and application thereof |
| CN105017746B (en) * | 2015-07-14 | 2017-10-10 | 河南大学 | A kind of functional nano SiO2/ polypropylene carbonate composite material and preparation method thereof |
| CN105838384B (en) * | 2016-04-27 | 2019-03-15 | 河南大学 | Renovation agent and preparation method thereof is passivated by the soil of carrier of nano silica |
| CN110194949B (en) * | 2018-02-27 | 2021-05-14 | 中国石油化工股份有限公司 | Hypotonic oil field pressure-reducing injection-increasing chemical agent and preparation method thereof |
| CN110643214B (en) * | 2019-10-24 | 2021-11-19 | 广州市飞雪材料科技有限公司 | High-dispersity precipitated silica anti-settling agent for coating and preparation method thereof |
| CN117229762A (en) * | 2023-08-30 | 2023-12-15 | 国网湖北省电力有限公司武汉供电公司 | Freezing solution for intelligent cooling device, preparation method and application thereof |
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|---|---|---|---|---|
| US6129949A (en) * | 1995-11-10 | 2000-10-10 | Hoecsht Research & Technology Deutschland Gmbh & Co Kg | Process for preparing organically modified aerogels using alcohols, wherein the resultant salts are precipitated |
| CN1303885A (en) * | 1999-10-25 | 2001-07-18 | 上海绿纳科技有限公司 | Preparation of nanometer composite particles-organic polymer mixed composite system |
| CN1386784A (en) * | 2002-05-23 | 2002-12-25 | 复旦大学 | Process for preparing SiO2-polymer composite material |
| CN1552760A (en) * | 2003-12-19 | 2004-12-08 | 清华大学 | Carboxyl functional polymer/SiO2 composite nanometer particle and preparing method thereof |
-
2004
- 2004-03-12 CN CNB2004100101244A patent/CN100341781C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6129949A (en) * | 1995-11-10 | 2000-10-10 | Hoecsht Research & Technology Deutschland Gmbh & Co Kg | Process for preparing organically modified aerogels using alcohols, wherein the resultant salts are precipitated |
| CN1303885A (en) * | 1999-10-25 | 2001-07-18 | 上海绿纳科技有限公司 | Preparation of nanometer composite particles-organic polymer mixed composite system |
| CN1386784A (en) * | 2002-05-23 | 2002-12-25 | 复旦大学 | Process for preparing SiO2-polymer composite material |
| CN1552760A (en) * | 2003-12-19 | 2004-12-08 | 清华大学 | Carboxyl functional polymer/SiO2 composite nanometer particle and preparing method thereof |
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| CN1666953A (en) | 2005-09-14 |
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