CN1207328A - Bulk sol-gel technique - Google Patents
Bulk sol-gel technique Download PDFInfo
- Publication number
- CN1207328A CN1207328A CN 98116544 CN98116544A CN1207328A CN 1207328 A CN1207328 A CN 1207328A CN 98116544 CN98116544 CN 98116544 CN 98116544 A CN98116544 A CN 98116544A CN 1207328 A CN1207328 A CN 1207328A
- Authority
- CN
- China
- Prior art keywords
- sol
- thf
- tetrahydrofuran
- gel technique
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Silicon Compounds (AREA)
Abstract
A bulk sol-gel process for preparing high-purity optical SiO2 material has the advantages of simple process, short process flow, controllable shape, not cracking, less volume shrink, and the power to bury any organic function moleculae in it.
Description
The present invention is a bulk sol-gel technique.
Sol-gel process is to be used to produce oxide compound (as: silicon-dioxide) stupalith that has controlled architecture and composition and a kind of method of hybrid inorganic-organic materials.Usually it be by metal alkoxides give polymers hydrolysis, ageing, solidify, condensation, dehydration and densification realize.Because to have processing temperature low, product is even and purity is high, moulding process can variation etc. characteristics.Therefore not only can invent many new materials and the performance of improving current material, various at high temperature unavailable materials can be implemented at normal temperatures apace.Yet, on technology,, mix except that because of using a large amount of solvents to cause the raw materials cost rising, gelation, a whole set of preparation time of ageing and exsiccant needs 20 days to 1 year, and small product size is shunk more than 90%, also often occurs with crack performance.Therefore, people are constantly studying for preparation oxide compound monolithic under the normal temperature.
In order to obtain not have the be full of cracks monolithic, the supercritical drying drying method, chemical drying promoter method, " heavily processing " method that increases the micro-pore diameter of gel is invented and is used.In addition, Wei carries out sol gel reaction by the alkoxyl silicone (TEOS) of methacrylic acid two alcohol esters and hydrolysis, and radical polymerization has obtained to be punctured into 6-20% then, and contains 50% silica sol-gel system.Ellsworth etc. replace alkoxyl group among the TEOS with polymerisable-oxyl functional group, can discharge polymerisable monomer after making compound hydrolysis, carry out polymerization in the presence of initiator, obtain SiO at last
2-polymer composites.Clark and his colleagues add inorganic salt in sol system, have shortened gelation time greatly.Yet none can have following characteristics simultaneously these systems: at the bottom of the processing temperature, volumetric shrinkage is little, and not having be full of cracks and oxide content is more than 50%.
The present invention utilizes in the carbonate and acid silicon dioxide sol solution at normal temperatures, to quicken gelation process, and adopt organic solvent under the synergy of carbonate, the solvent (as: THF) that uses when hydrolysis alcoxyl silicon gives polymers is fallen in extraction, to eliminate solvent evaporation is ageing process, thereby technical process is shortened, volumetric shrinkage reduces, but the bulk sol liquid direct pouring moulding that obtains, also can carry out second casting, the silicon-dioxide bulk sol that had both obtained mixes mutually with silicon dioxide particles, again casting.Obtain having the silica monoliths of different shape after the drying.These high-purity silicon dioxides can be used to prepare the high-accuracy optical material of high-performance.In addition, add organic functional molecular after, and even can obtain photochromic, electrochromism electricity and lead and ionic conducting glass, also can be used for various transmitters, catalyzer and organic synthesis carrier etc.As seen, the present invention has that the preparation route is simple, easy to operate, and flow process is short, and the earth silicon material type shape that obtains is controlled, does not have be full of cracks, and volumetric shrinkage is little, and can imbed any organic functional molecular, makes characteristics such as its opticglass is more widely used.
The present invention adopts alkoxy-silicon compound Si (OC
nH
2n+1)
4, water, hydrochloric acid (2M), tetrahydrofuran (THF) is 1: 2.5: 0.01 according to mol ratio: 3 at room temperature mix stirring, until the disappearance that is separated, at 60 ℃ of following backflow 2-3 hours, obtain sol solution then.This solution neutralizes with carbonate, and carbonate can be an alkali metal salt, also can be divalent salts, for example: Li
+, Na
+, K
+, Be
++, Ba
++, Cr
++, Ca
++, Cu
++, Pb
++, Zn
++, Mg
++, wherein performance the best is Quilonum Retard.Mix 3-60 second mutually, leach remaining carbonate powder with filter paper then, collect this sol solution in a separating funnel, add organic solvent and be used to extract tetrahydrofuran (THF).Organic solvent comprise all can form two-phase with sol solution and with tetrahydrofuran (THF) with arbitrarily than the solvent of blend, as benzene, toluene, dimethylbenzene, pentane, hexane, heptane, hexanaphthene.That best is hexanaphthene (10ml-50ml), and it is static to rock three reliefs, treats the appearance that is separated, and collects the bottom body sol liquid.This colloidal sol is injected mould, seal with Parafilm, and make several pin holes on film, be 3 seconds to 3 days set time at normal temperatures, and placing and obtaining purity after 15 days is 70-95%, and volumetric shrinkage is the silica monoliths of 5-45%.According to mold shape, they can be round, column, strip, sheet.When sol solution and extraction liquid are transferred in the round-bottomed flask together, and when carrying out mechanical stirring, we can also obtain ball-type particle (φ: 10nm-5mm).
Embodiment 1
Add the 31.5g tetraethoxy-silicane at the 250ml round-bottomed flask, 6.75g water, 0.75ml hydrochloric acid (2M), the 21.5g tetrahydrofuran (THF) at room temperature stirs 15 minutes until the disappearance that is separated that occurs, then at 60 ℃ of following backflow 2-3 hours.The silicon dioxide gel solution (5g) that obtains mixes mutually with Quilonum Retard (1.2g), and stirs for 3 seconds, filters out the Quilonum Retard powder that is not neutralized then, obtains sol solution.
Get this solution of 5g and pack into and have in three mouthfuls of round-bottomed flasks of churned mechanically 100ml, add the 20ml hexanaphthene, (1000 rev/mins) are stirred in beginning fast, and diameter is that 50 micron silica particles occur after 10 minutes, removes hexanaphthene, is allowed to condition under the room temperature dry.Other gets the 5g sol solution and puts into separating funnel, adds the 20ml hexanaphthene, rocks 3 times, and the body silicon dioxide gel of bottom is collected in the appearance that is separated.
With 5g SiO
2Particle and 1g SiO
2The bulk sol liquid mixing is injected in the vial, covers and seals film, sting 7 apertures, begin after 5 minutes to solidify.Place the thermogravimetic analysis (TGA) that records after 15 days and show that the solid disk of formation contains 91% silicon-dioxide, volumetric shrinkage is 5%.Embodiment 2
Make silicon-dioxide bulk sol liquid according to embodiment 1.Get this liquid of 5g, mix mutually with the 1.2g Quilonum Retard, and stirred for 3 seconds, filter out the Quilonum Retard powder that is not neutralized then.Surplus solution is collected in the separating funnel, adds the 20ml hexanaphthene, rocks 3 times, and the body silicon dioxide gel of bottom is collected in the appearance that is separated.In the injection vial, cover and seal film, sting 7 apertures, begin after 5 minutes to solidify.Place the thermogravimetic analysis (TGA) that records after 15 days and show that the solid disk of formation contains 89% silicon-dioxide, volumetric shrinkage is 40%.Embodiment 3
According to embodiment 1 preparation silicon-dioxide bulk sol liquid, get this liquid 5g and mix mutually, and stirred for 3 seconds with the 1g Quilonum Retard, filter the back and extract with the 20ml hexanaphthene.The body silicon dioxide gel of collecting was at 24 hours after fixing.Place after 15 days, obtain a disk that contains 85% silicon-dioxide, volumetric shrinkage is 30%.Embodiment 4
According to embodiment 2 preparation silica monolithses.Wherein replace tetraethoxy-silicane with tetramethoxy-silicane, the result who obtains is identical with embodiment 2.Embodiment 5
According to embodiment 1 preparation silicon-dioxide bulk sol liquid.Get this solution 5g and mix mutually, and stirred for 3 seconds, filter the back and extract with the 20ml hexanaphthene with 1.2g yellow soda ash.The body silicon dioxide gel of collecting was at 3 hours after fixing.Place after 15 days, obtain a disk that contains 80% silicon-dioxide, volumetric shrinkage is 30%.Embodiment 6
According to embodiment 2 preparation silica monolithses.Wherein Skellysolve A is replaced hexanaphthene, the result who obtains is identical with embodiment 2.Embodiment 7
According to embodiment 1 preparation silicon-dioxide bulk sol liquid.Get the 0.08g Quilonum Retard and mix mutually with the 5g sol liquid, and stir several seconds, filter out remaining salt end then, solution is collected in 250ml and is equipped with in churned mechanically three mouthfuls of round-bottomed flasks.The 20ml hexanaphthene is added in the flask, and fast stating begins to stir, and diameter is the silicon dioxide granule appearance of 0.6mm after 10 minutes, removes hexanaphthene, is allowed to condition under the room temperature dry.Dioxide-containing silica is 95%.
Claims (4)
1. the invention belongs to bulk sol-gel technique, it is characterized in that adopting Si (OC
nH
2n+1)
4Water, hydrochloric acid (2M), tetrahydrofuran (THF) at room temperature mixes stirring, until the disappearance that is separated, obtained sol solution then at 60 ℃ of following backflow 2-3 hours, this solution neutralizes with carbonate and mixes mutually 3-60 second, leach the powder of carbonate then, collect sol solution in separating funnel, add the organic solvent extraction tetrahydrofuran (THF), bottom colloidal sol is injected mould, seal with Parafilm, and on film, make several pin holes, solidified at normal temperatures 3 seconds to 3 days, and placed and obtained the high 70-95% of being of purity in 15 days afterwards, volumetric shrinkage is the silica monoliths of 5-45%, when sol solution and extraction agent are transferred in the round-bottomed flask together, and when carrying out mechanical stirring, can obtain ball-type particle (φ: 10nm-5mm).
2. as right 1 described bulk sol-gel technique, it is characterized in that Si (OC
nH
2n+1)
4, water, hydrochloric acid (2M), tetrahydrofuran (THF) mol ratio be 1: 2.5: 0.01: 3.
3. as right 1 described bulk sol-gel technique, it is characterized in that used carbonate is an alkali metal salt, also can be divalent salts, for example Li
+, Na
+, K
+, Be
++, Ba
++, Cr
++, Ca
++, Cu
++, Pb
++, Zn
++, Mg
++, wherein performance the best is Quilonum Retard.
4. as right 1 described bulk sol-gel technique, the organic solvent that it is characterized in that extracting tetrahydrofuran (THF) is benzene,toluene,xylene, pentane, hexane, heptane, hexanaphthene, and wherein hexanaphthene is best.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98116544A CN1085557C (en) | 1998-08-04 | 1998-08-04 | Bulk sol-gel technique |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98116544A CN1085557C (en) | 1998-08-04 | 1998-08-04 | Bulk sol-gel technique |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1207328A true CN1207328A (en) | 1999-02-10 |
| CN1085557C CN1085557C (en) | 2002-05-29 |
Family
ID=5225132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98116544A Expired - Fee Related CN1085557C (en) | 1998-08-04 | 1998-08-04 | Bulk sol-gel technique |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1085557C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105699C (en) * | 1999-09-02 | 2003-04-16 | 吉林大学 | Compound mass sol-gel preparation process |
| CN1111133C (en) * | 2001-06-21 | 2003-06-11 | 吉林大学 | One-component sol-gel technique |
| CN102167398A (en) * | 2011-03-16 | 2011-08-31 | 奇瑞汽车股份有限公司 | Preparation method of normal-temperature-cured titanium dioxide sol |
| CN102294255A (en) * | 2010-06-25 | 2011-12-28 | 中国科学院大连化学物理研究所 | Carbon gel catalyst and application thereof |
| CN109158060A (en) * | 2018-10-11 | 2019-01-08 | 沈阳师范大学 | A kind of preparation method and application for the gradient color no cracking gel indicating light application time |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5196382A (en) * | 1985-02-25 | 1993-03-23 | University Of Florida Research Foundation, Inc. | Method for rapid production of large sol-gel SiO2 containing monoliths of silica with and without transition metals |
| US4851373A (en) * | 1985-02-25 | 1989-07-25 | University Of Florida | Large sol-gel SiO2 monoliths containing transition metal and their production |
| US5328645A (en) * | 1989-01-04 | 1994-07-12 | Ppg Industries, Inc. | Gel promoters for silica sols |
| CN1058908C (en) * | 1997-06-20 | 2000-11-29 | 清华大学 | Method for prepn. of ultra filtering silica membrane used for seawater desalination |
-
1998
- 1998-08-04 CN CN98116544A patent/CN1085557C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105699C (en) * | 1999-09-02 | 2003-04-16 | 吉林大学 | Compound mass sol-gel preparation process |
| CN1111133C (en) * | 2001-06-21 | 2003-06-11 | 吉林大学 | One-component sol-gel technique |
| CN102294255A (en) * | 2010-06-25 | 2011-12-28 | 中国科学院大连化学物理研究所 | Carbon gel catalyst and application thereof |
| CN102294255B (en) * | 2010-06-25 | 2014-08-06 | 中国科学院大连化学物理研究所 | Carbon gel catalyst and application thereof |
| CN102167398A (en) * | 2011-03-16 | 2011-08-31 | 奇瑞汽车股份有限公司 | Preparation method of normal-temperature-cured titanium dioxide sol |
| CN109158060A (en) * | 2018-10-11 | 2019-01-08 | 沈阳师范大学 | A kind of preparation method and application for the gradient color no cracking gel indicating light application time |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1085557C (en) | 2002-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100556800C (en) | A kind of multilevel ordered mesoporous/macropore complex carbon material and preparation method thereof | |
| CN101646622A (en) | The method and the hydrophobic aerogel prepared therefrom that prepare hydrophobic aerogel | |
| CN102502667B (en) | Large-pore-diameter large-window three-dimensionally communicated ordered mesoporous material and preparation method thereof | |
| CN107215885B (en) | A kind of inorganic polyions cluster and its preparation method and application | |
| CN102372734A (en) | Synthesis of novel nano hybrid reinforcing agent containing POSS | |
| CN1085557C (en) | Bulk sol-gel technique | |
| CN103214675A (en) | Poly(methylsilane-carbosilane) and preparation method thereof | |
| CN103936442A (en) | Composition and preparation method of magnesium-yttrium-calcium compound stabilized zirconia nozzle brick | |
| CN101735633A (en) | Functionalized organic/inorganic hybridized asymmetric structure particle and synthesis method thereof | |
| JPH09110989A (en) | Formed organopolysiloxane containing sulfonate and mercapto groups, production thereof, and condensation catalyst and bisphenol a synthesis catalyst which comprise the oranosiloxane or contain it | |
| Huang et al. | New hybrid materials incorporating tetrabutyl titanate and tetraethoxysilane with functional SEBS elastomer via the sol‐gel process: Synthesis and characterization | |
| CN112194144A (en) | Preparation method of spherical silicon micropowder | |
| Wang et al. | A novel bulk sol-gel process to prepare monolithic silica materials | |
| CN1304871A (en) | Dual-pore molecular sieve and its preparing process | |
| CN1105699C (en) | Compound mass sol-gel preparation process | |
| KR100262141B1 (en) | Method for the preparation of small ceramic bead | |
| CN1111133C (en) | One-component sol-gel technique | |
| CN87101502A (en) | Producing modified organic water-glass bonder | |
| KR100282990B1 (en) | Manufacturing method of silicone resin | |
| CN103877941A (en) | Spherical silicon-based organic-inorganic hybrid boron adsorbent and preparation method thereof | |
| CN101117558A (en) | Gel injection molding material composition for aluminium silicon carbide integrated circuit pipe shell and method for preparing products | |
| CN100457409C (en) | In situ inductive coagulating formative process for mullite-based ceramic by hydrolysis | |
| JPS61204033A (en) | Granulating method for powder of inorganic raw material | |
| CN1331870C (en) | Epoxy-silsesquioxanes preparation method | |
| CN109516727A (en) | A kind of corrosion-resistant cement pipe pile of photovoltaic and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |