CN101428807A - Process for producing easily dispersable duoparental nano-silicon dioxide - Google Patents
Process for producing easily dispersable duoparental nano-silicon dioxide Download PDFInfo
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- CN101428807A CN101428807A CNA2008101595470A CN200810159547A CN101428807A CN 101428807 A CN101428807 A CN 101428807A CN A2008101595470 A CNA2008101595470 A CN A2008101595470A CN 200810159547 A CN200810159547 A CN 200810159547A CN 101428807 A CN101428807 A CN 101428807A
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Abstract
A method for preparing amphiphilic nano silicon dioxide with good dispersity has main technical characteristics that a sodium silicate water solution with silicon dioxide weight content being 25-30% is heated to 50-60 DEG C, a titanic acid ester coupling agent is added, and stirring is performed evenly at a constant temperature; then dilute hydrochloric acid is slowly added at an even speed until the pH value reaches 8-9, and stirring is performed for 1 h; the temperature is risen to 70-80 DEG C, the titanic acid ester coupling agent is added according to 50% of the first adding amount, stirring is performed for 30 minutes, dilute hydrochloric acid is slowly added at an even speed again until the pH value of the reaction system reaches 6-7, the temperature is kept, and stirring is performed for 1 h; and the amphiphilic nano silicon dioxide powder with good dispersity can be obtained after the reaction solution is filtered, washed, heated and dried. The product has good amphiphilic performance, so as to be well compatible with organic matters in the added system, and have good hydrophilicity. The product only needs common dispersing or grinding equipment to disperse well in the nano state in the added system.
Description
Technical field
The present invention relates to a kind of preparation method of easily dispersable duoparental nano-silicon dioxide.
Background technology
Nano silicon is commonly called as " ultra-fine white carbon black ", because of its volume effect and surface effects in magnetic, electrically, catalytic performance, absorption property, photoabsorption, aspects such as thermal resistance present specific performance, be widely used in catalyzer, petrochemical complex, discoloring agent, matting agent, rubber reinforcing filler, filler for plastic, printing ink thickening material, the soft polishing agent of metal, the insulation and thermal insulation weighting agent, various fields such as high-grade daily-use makeup filler and spray material have wide application field and development potentiality, more and more be subjected to people's attention and attention in recent years, enjoy " industrial monosodium glutamate ", the good reputation of " initial point of Materials science ".Because nano particle has great specific surface area and higher surface energy, particle aggregation very easily takes place in preparation and use, form offspring, make particle diameter become big, thereby influencing nano particle greatly makes the most of the advantage, lose the function that nano particle possesses, brought difficulty for the use of nano silicon.
Preparation method of nano silicon dioxide mainly contains vapor phase process, sol-gel method and precipitator method three major types, the characteristics of having nothing in common with each other at present.Adopt vapor phase process to produce nano silicon, related invention patent such as CN1422805A.The common ground of these class methods is complex process, and facility investment is big, the production cost height, and the scale operation difficulty is big, and the product price height has greatly limited the Application Areas and the scope of product.
Adopt the Prepared by Sol Gel Method nano silicon, related invention patent such as CN1458064A are that SiO is prepared in hydrolyzed silicate ester-polycondensation
2Colloidal sol, and then generate SiO
2Gel is with SiO
2Gel ageing, drying make nano silicon.
Adopt the precipitator method to prepare nano silicon, related invention patent such as CN1626440A are in alkali metal silicate solutions, add water-soluble polymers and/or water-soluble C
1～C
8Organic alcohol uses organic monoacid as hydrolytic precipitation Preparation of Catalyst nano silicon.Patent CN1524786A is with SiO
2Colloidal sol is raw material, after sour environment and low-carbon alcohol are dissolved each other, produces nano silicon through precipitin reaction.Patent CN1634763A adopts chemical direct synthesis technique, adds entry and additive in advance in raw material, produces nano high purity silicon-dioxide with water glass and sulfuric acid reaction.Patent CN1631777A is raw material with the silicon sol, under the effect of ionic and nonionic surface active agent and other additive, and the pH value of regulator solution, obtain nano silica powder by spraying drying.Patent CN1865137A joins alkalimetal silicate in the mixture of hydrocarbon component, tensio-active agent and cosurfactant, form the super solubilising micelle of the nanometer system of oil bag high concentration alkali metal silicate, the nano silicon that is produced is limited in carries out precipitin reaction in the nanometer micelle, obtain nano silicon through washing, drying.
Problems such as different method for preparing nano silica has characteristics separately, and the unsuitable industrialization of some existence in various degree, complex process, facility investment height, production cost are higher.Prior some product cut size is bigger than normal, product particle is reunited serious, the user is difficult to open it with common dispersing and mixing means, do not reach the due effect of nanometer product in actual the use, producing the major cause of these problems, is because nano particle has great specific surface area and higher surface energy, in preparation and use particle aggregation takes place very easily, form offspring, make particle diameter become big.In addition, most nano silicons are difficult to be directly used in organic system without surface modification, do not have parents' performance, have increased the application difficulty, have greatly limited the Application Areas of product.Therefore the exploitation and the production of easily dispersable duoparental nano-silicon dioxide become crucial in recent years applied research topic.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of easily dispersable duoparental nano-silicon dioxide, when nano-silicon dioxide particle forms, promptly carry out in-situ modified to particle surface, insert different organic groups, reduce the surface hydroxyl of silicon dioxide granule, thereby reduce the surface energy of particle, the reunion that alleviates nano-silicon dioxide particle makes nano silica powder be easy to disperse.
The preparation method of easily dispersable duoparental nano-silicon dioxide of the present invention is characterized in that comprising the steps:
(1) with silicon-dioxide quality content is 25～30% sodium silicate aqueous solution, is warming up to 50～60 ℃, press 0.05～10% of aqueous solution weight and add titanate coupling agent, stir under the constant temperature;
(2) single step reaction: dilute hydrochloric acid is slowly at the uniform velocity added above-mentioned finishing in the sodium silicate aqueous solution that constant temperature stirs in 10～60min, to PH be 8～9, stop to add acid, stir 1h;
(3) two steps reaction: continue to be warmed up to 70～80 ℃, add titanate coupling agent once more, stir 30min by 50% of first add-on, slowly at the uniform velocity add dilute hydrochloric acid with identical speed once more, pH value up to reaction system is 6～7, stops to add acid, keeps temperature and stirs 1h;
(4) with reacting liquid filtering, washing is heated to 110～180 ℃ with the precipitated silica after the washing in vacuum drying oven, and dry 4～6 hours, or, promptly obtain the easily dispersable duoparental nano-silicon dioxide powder at microwave drying oven inner drying 20～60min.
Described titanate coupling agent can be selected one or more in the following material: two (dioctylphyrophosphoric acid ester) oxyacetate titanic acid ester, chelating phosphoric acid ester titanium coupling agent quaternary amine, two (two octyloxy pyrophosphates) ethylene titanic acid ester and trolamine inner complex, hydramine type titanic acid ester.
The mass concentration of described dilute hydrochloric acid is 12～15%.
The present invention is directed to fumed nano silicon-dioxide preparing technique process complexity, facility investment is big, high energy consumption, expensive problem, and the nano silicon product of common precipitator method preparation exists, and particle diameter is big, reunion is serious, be difficult for a dispersive difficult problem, and a kind of preparation method of easily dispersable duoparental nano-silicon dioxide is provided.
The present invention is raw material with the water glass, reacts with hydrochloric acid, in the nano silicon preparation feedback process, adopt in-situ modified technology, utilize the stepwise reaction method, introduce many groups tensio-active agent, when nano-silicon dioxide particle forms, promptly carry out in-situ modified to particle surface, insert different organic groups, reduce the surface hydroxyl of silicon dioxide granule, thereby reduce the surface energy of particle, alleviate the reunion of nano-silicon dioxide particle, make nano silica powder be easy to disperse.Because the introducing of different organic groups, the synthetic nano silica powder is when disperseing and use, existing good hydrophilicity, well compatible with organic substance again, good interface is arranged, thereby make product have parents' performance preferably, product is widely used in various fields such as senior speciality coating, specialty elastomer, superior cosmetics, medicine, extraordinary catalyzer, complete alternative imported product.
Advantage of the present invention:
Adopt in-situ modified technology, utilize the stepwise reaction method, introduce many groups tensio-active agent, the hydroxyl with organic group replacement silica particle surface has prepared easily dispersable duoparental nano-silicon dioxide.Product SiO
2〉=99.9%, particle diameter is little, between 15-30nm, and particle aggregation significantly reduces, and powder dispersity is good, only needs common dispersing apparatus in the use, can be distributed to the nanometer state.Product has parents' performance preferably, can be well compatible with the organic substance in the institute interpolation system, have good hydrophilicity again.Nano silica powder after the modification only need be with common dispersion or grinding plant, can be well be dispersed in the middle of the system of being added with the nanometer state.Nano silicon after the modification directly is separated into nano dispersion fluid, and stable performance has the high dispersive performance, and the user can directly add use.Solve different user and in use disperseed difficult problem.
Technical process of the present invention is short, number of devices is few, be easy to control and operation, and production cost is low, and constant product quality is easy to suitability for industrialized production, environmentally safe.
Description of drawings
Fig. 1 is embodiment 1 nano silicon aqueous dispersions electromicroscopic photograph figure.
Embodiment
Embodiment 1:
(1) sodium silicate aqueous solution with 600g25wt% joins in the 1000ml three-necked flask, and controlled temperature is at 52 ± 2 ℃.Add two (dioctylphyrophosphoric acid ester) the oxyacetate titanic acid ester of 12g, keep temperature and stir 1h.
(2) single step reaction: slowly at the uniform velocity splash into the hydrochloric acid (dripping off in 40min) of 12% (wt), the reaction solution pH value is adjusted at 8 o'clock, stops to add acid, and constant temperature stirs 1h.
(3) two step reactions: continue to be warming up to 75 ± 2 ℃, add two (dioctylphyrophosphoric acid ester) the oxyacetate titanic acid ester of 6g, stir 30min, slowly at the uniform velocity splash into the dilute hydrochloric acid of 12% (wt) once more, be adjusted at 6 o'clock, stop to add acid up to the pH value of reaction system.Keep constant temperature, stir 1h.
(4) with reacting liquid filtering, washing.
(5) precipitated silica after will washing is heated to 180 ℃ in vacuum drying oven, and dry 4 hours, promptly obtain the easily dispersable duoparental nano-silicon dioxide powder, powder purity is 99.9%, particle diameter is between 15-25nm.Particle with this nano-scale is dispersed in water, ethanol, acetone, toluene or the vinylbenzene, and dispersion liquid solid content (quality) is 20%, stable performance, does not reunite.Powder is the nanoparticle dispersion liquid of 15～25nm that dispersion obtains in common mulser.The aqueous dispersions electromicroscopic photograph is seen Fig. 1.By photo as can be seen, the dispersion liquid good dispersity, relatively evenly.
Embodiment 2:
(1) sodium silicate aqueous solution with 600g30% (wt) joins in the 1000ml three-necked flask, and controlled temperature is at 55 ± 2 ℃.Add two (two octyloxy pyrophosphates) the ethylene titanic acid ester of 20g, keep temperature and stir 1h.
(2) single step reaction: slowly at the uniform velocity splash into the hydrochloric acid (dripping off in 20min) of 15% (wt), the reaction solution pH value is adjusted at 8 o'clock, stops to add acid, and constant temperature stirs 1h.
(3) two step reactions: continue to be warming up to 75 ± 2 ℃, add two (two octyloxy pyrophosphates) the ethylene titanic acid ester of 10g, stir 30min, slowly at the uniform velocity splash into 15% dilute hydrochloric acid once more, be adjusted at 6.5 o'clock, stop to add acid up to the pH value of reaction system.Keep constant temperature, stir 1h.
(4) with reacting liquid filtering, washing.
(5) precipitated silica after will washing is heated to 160 ℃ in vacuum drying oven, and dry 6 hours, promptly obtain easily dispersable duoparental nano-silicon dioxide, powder purity is 99.93%, particle diameter is between 15-30nm.Particle with this nano-scale is dispersed in water, ethanol, hexanaphthene, benzene or the vinylbenzene, and the dispersion liquid solid content is 30%, stable performance, does not reunite.Powder is the nanoparticle dispersion liquid of 15～30nm that dispersion obtains in common stirring tank.
Embodiment 3:
(1) sodium silicate aqueous solution with 600g25% (wt) joins in the 1000ml three-necked flask, and controlled temperature is at 58 ± 2 ℃.Add 20g chelating phosphoric acid ester titanium coupling agent quaternary amine, keep temperature and stir 1h.
(2) single step reaction: slowly at the uniform velocity splash into the hydrochloric acid (dripping off in 50min) of 12% (wt), the reaction solution pH value is adjusted at 8.5 o'clock, stops to add acid, and constant temperature stirs 1h.
(3) two step reactions: continue to be warming up to 78 ± 2 ℃, add 10g chelating phosphoric acid ester titanium coupling agent quaternary amine, stir 30min, slowly at the uniform velocity splash into 12% dilute hydrochloric acid once more, be adjusted at 6 o'clock, stop to add acid up to the pH value of reaction system.Keep constant temperature, stir 1h.
(4) with reacting liquid filtering, washing.
(5) the precipitated silica dry 20min in microwave drying oven after will washing promptly obtains easily dispersable duoparental nano-silicon dioxide, and powder purity is 99.92%, and particle diameter is between 15-25nm.Particle with this nano-scale is dispersed in water, ethanol, benzene, vinylbenzene or the methacrylic ester, and the dispersion liquid solid content is 25%, stable performance, does not reunite.Powder is the nanoparticle dispersion liquid of 15～25nm that dispersion obtains in common mulser.
Claims (3)
1, a kind of preparation method of easily dispersable duoparental nano-silicon dioxide is characterized in that comprising the steps:
(1) with silicon-dioxide quality content is 25～30% sodium silicate aqueous solution, is warming up to 50～60 ℃, press 0.05～10% of aqueous solution weight and add titanate coupling agent, stir under the constant temperature;
(2) single step reaction: dilute hydrochloric acid is slowly at the uniform velocity added above-mentioned finishing in the sodium silicate aqueous solution that constant temperature stirs in 10～60min, to PH be 8～9, stop to add acid, stir 1h;
(3) two steps reaction: continue to be warmed up to 70～80 ℃, add titanate coupling agent once more, stir 30min by 50% of first add-on, slowly at the uniform velocity add dilute hydrochloric acid with identical speed once more, pH value up to reaction system is 6～7, stops to add acid, keeps temperature and stirs 1h;
(4) with reacting liquid filtering, washing is heated to 110～180 ℃ with the precipitated silica after the washing in vacuum drying oven, and dry 4～6 hours, or, promptly obtain the easily dispersable duoparental nano-silicon dioxide powder at microwave drying oven inner drying 20～60min.
2, preparation method according to claim 1 is characterized in that described titanate coupling agent selects one or more in the following material: two (dioctylphyrophosphoric acid ester) oxyacetate titanic acid ester, chelating phosphoric acid ester titanium coupling agent quaternary amine, two (two octyloxy pyrophosphates) ethylene titanic acid ester, trolamine inner complex or hydramine type titanic acid ester.
3, preparation method according to claim 1, the mass concentration that it is characterized in that described dilute hydrochloric acid is 12～15%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104150490A (en) * | 2014-08-19 | 2014-11-19 | 确成硅化学股份有限公司 | Preparation method of nanometer silica |
| CN106221605A (en) * | 2016-07-26 | 2016-12-14 | 安徽敬业纳米科技有限公司 | A kind of preparation method of adhesive parental type nano silicon |
| CN106753730A (en) * | 2016-12-16 | 2017-05-31 | 池州市旭豪机械有限公司 | A kind of Steel Tube Rolling core rod lubricant agent |
| CN110330022A (en) * | 2019-07-08 | 2019-10-15 | 福建远翔新材料股份有限公司 | A kind of preparation method of foamed silastic sponge high dispersive silica |
| CN110668450A (en) * | 2019-11-14 | 2020-01-10 | 陈淑英 | High-dispersity nano silicon dioxide and preparation method thereof |
| US10682619B2 (en) | 2017-08-09 | 2020-06-16 | Petrochina Company Limited | Nano-silica dispersion having amphiphilic properties and a double-particle structure and its production method |
-
2008
- 2008-11-27 CN CNA2008101595470A patent/CN101428807A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104150490A (en) * | 2014-08-19 | 2014-11-19 | 确成硅化学股份有限公司 | Preparation method of nanometer silica |
| CN104150490B (en) * | 2014-08-19 | 2016-06-22 | 确成硅化学股份有限公司 | The preparation method of nano silicon |
| CN106221605A (en) * | 2016-07-26 | 2016-12-14 | 安徽敬业纳米科技有限公司 | A kind of preparation method of adhesive parental type nano silicon |
| CN106753730A (en) * | 2016-12-16 | 2017-05-31 | 池州市旭豪机械有限公司 | A kind of Steel Tube Rolling core rod lubricant agent |
| US10682619B2 (en) | 2017-08-09 | 2020-06-16 | Petrochina Company Limited | Nano-silica dispersion having amphiphilic properties and a double-particle structure and its production method |
| CN110330022A (en) * | 2019-07-08 | 2019-10-15 | 福建远翔新材料股份有限公司 | A kind of preparation method of foamed silastic sponge high dispersive silica |
| CN110668450A (en) * | 2019-11-14 | 2020-01-10 | 陈淑英 | High-dispersity nano silicon dioxide and preparation method thereof |
| CN110668450B (en) * | 2019-11-14 | 2021-07-16 | 德化月记窑陶瓷有限责任公司 | High-dispersity nano silicon dioxide and preparation method thereof |
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Open date: 20090513 |