CN1600786A - Method for preparing organic silicon compound from amorphous silica - Google Patents
Method for preparing organic silicon compound from amorphous silica Download PDFInfo
- Publication number
- CN1600786A CN1600786A CN 03135078 CN03135078A CN1600786A CN 1600786 A CN1600786 A CN 1600786A CN 03135078 CN03135078 CN 03135078 CN 03135078 A CN03135078 A CN 03135078A CN 1600786 A CN1600786 A CN 1600786A
- Authority
- CN
- China
- Prior art keywords
- silicoorganic compound
- residue
- soft silica
- distillation reaction
- silica
- 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
Images
Landscapes
- Silicon Compounds (AREA)
Abstract
The characteristic is that precipitation white carbon and residue of nonmetal ore extracted metal ion with amorphous silicon dioxide as main composition are used as silicon contained raw material. In alkali metal hydroxide medium or alkaline-earth metal hydroxide medium, there are silicon contained raw materials and orthoglycol which are generated organic silicon compound by distilling reaction.
Description
Technical field:
The present invention relates to a kind of preparation method of silicoorganic compound.
Background technology:
Traditional organosilicon synthetic method is that quartz is reduced to elemental silicon under 1200 ℃ of high temperature, makes the silicon alkyl halide with halohydrocarbons reaction more then in the presence of catalyzer, makes different silicoorganic compound at last more as required.This method exists long reaction time, pilot process complexity, shortcoming such as energy consumption is big.
Articles synthetic five by silicon-dioxide, the sexadentate silicoorganic compound that people such as R.M.Laine have delivered in 1991 directly, method therefor has solved the deficiency that exists in traditional organosilicon synthetic method preferably, the silicoorganic compound of gained can not only be used to produce traditional organosilicon material, can also be used to produce many useful new chemical materialses.Yet the direct method by silicon-dioxide synthesizing organo-silicon compound of report remains in some shortcomings at present: the one, and at present synthetic used raw material is silica gel, molten silicon and gas-phase silica, and theirs is on the high side, reaches 60,000 yuan/ton as gas-phase silica.The existence of this problem can directly influence production cost and the competitive power of product on market; The 2nd, synthetic used method is the general heating method under the nitrogen protection, and the reaction times is still longer.
Summary of the invention:
Technical problem to be solved by this invention is to avoid above-mentioned existing in prior technology weak point, provides that a kind of raw materials cost is low, the reaction times is short prepares the method for silicoorganic compound by soft silica.
The technical scheme that technical solution problem of the present invention is adopted is:
A kind of method for preparing silicoorganic compound by soft silica, be to be that the nonmetalliferous ore of major ingredient extracts residue behind the metal ion as silicon-containing material with precipitated silica or with the soft silica, in alkali metal hydroxide medium or alkaline earth metal oxide medium, silicon-containing material and adjacent glycol generate silicoorganic compound by distillation reaction.
The residue that nonmetalliferous ore among the present invention extracts behind the metal ion can be carried the magnesium residue for wilkinite residue of aluminum-extracted or serpentine; Alkali metal hydroxide can be sodium hydroxide, potassium hydroxide or lithium hydroxide etc.; Alkaline earth metal oxide can be barium oxide or calcium oxide etc.
The present invention extracts residue behind the metal ion as silicon-containing material with precipitated silica and nonmetalliferous ore, can adopt microwave heating method in its distillation reaction, preparation five, sexadentate silicoorganic compound.Compared with the prior art, it is low that beneficial effect of the present invention is embodied in its raw materials cost, and the reaction times is short.Wherein, the price of precipitated silica only is 0.5 ten thousand yuan/ton, and the price of residue is then lower behind nonmetalliferous ore (as wilkinite, serpentine) the extraction metal ion.
Show through modern instrumental analysises such as X-ray diffraction, infrared spectra, heat analyses, the main component that nonmetalliferous ore such as wilkinite, serpentine extracts the residue behind the metal ion is a soft silica, and, can make that dioxide-containing silica reaches higher degree in the residue by controlling nonmetalliferous ore leaching reaction conditions well.Because of this soft silica has high reaction activity and high, so be called active silica again.This residue has obtained applied research more widely at present, as produce 4 zeolites, water glass, white carbon black, metasilicate pentahydrate sodium, non-hydrate sodium metasilicate or the like with it.
In the alkali metal hydroxide medium, these silicon-containing materials can with the adjacent glycol of nucleophilic organic reagent, generating pentacoordinate body silicoorganic compound through distillation reaction, is example (obtaining the dimer of sodium salt usually) with ethylene glycol and sodium hydroxide, and its main chemical equation is:
SiO2+NaOH+3HO(CH2)2OH?
200℃?Na(OCH2CH2O)2SiOCH2CH2OH+3H2O
--------(1)
2Na(OCH
2CH
2O)
2SiOCH
2CH
2OH?
170℃?Na
2(OCH
2CH
2O)
2SiOCH
2CH
2OSi(OCH
2CH
2O)
2+HO(CH
2)
2OH
--------(2)
In alkaline earth metal oxide, these silicon-containing materials can with the adjacent glycol of nucleophilic organic reagent, generate the organic silicide of hexa-coordinate through distillation reaction, be example with ethylene glycol and barium oxide, its main chemical equation is:
SiO2+BaO+3HO(CH2)2OH?
200℃?BaSi(OCH2CH2O)3+3H2O
--------(3)
Fig. 1 is raw material for adopting the inventive method with the precipitated silica, the X-ray diffracting spectrum of synthetic gained pentacoordinate body silicoorganic compound (sodium salt).
Fig. 2 is raw material for adopting the inventive method with the wilkinite residue of aluminum-extracted, the X-ray diffracting spectrum of synthetic gained pentacoordinate body silicoorganic compound (sodium salt).
Fig. 3 is for adopting the inventive method, and carrying the magnesium residue with serpentine is raw material, the X-ray diffracting spectrum of synthetic gained pentacoordinate body silicoorganic compound (lithium salts).
Fig. 4 is raw material for adopting the inventive method with the precipitated silica, the X-ray diffracting spectrum of synthetic gained sexadentate silicoorganic compound (barium salt).
Fig. 5 is raw material for adopting the inventive method with the wilkinite residue of aluminum-extracted, the X-ray diffracting spectrum of synthetic gained sexadentate silicoorganic compound (barium salt).
Fig. 6 is for adopting the inventive method, and carrying the magnesium residue with serpentine is raw material, the X-ray diffracting spectrum of synthetic gained sexadentate silicoorganic compound (calcium salt).
Embodiment:
Embodiment 1:
The precipitated silica that takes by weighing 10g, granularity＜76 μ m is in flask, and the sodium hydroxide of stoichiometric ratios such as adding and 45-90mL ethylene glycol are specifically as follows 60mL; Mixing is placed in the microwave oven, distillation reaction is 25 minutes under 700W, take out flask, leave standstill crystallization, the gained solid phase prod washs with acetonitrile, be lower than then-0.05MPa, under the condition of 50-100 ℃ vacuum-drying 5-15 hour, specifically can be under-0.08MPa, 70 ℃ condition dry 6 hours; The X-ray diffracting spectrum of product as shown in Figure 1.As seen from the figure, this product is pentacoordinate body silicoorganic compound (sodium salt).
Embodiment 2:
The wilkinite residue of aluminum-extracted that takes by weighing 10g, granularity＜76 μ m is in flask, and the sodium hydroxide of stoichiometric ratios such as adding and 45-90mL ethylene glycol are specifically as follows 60mL; Mixing is placed in the microwave oven, and distillation reaction is 30 minutes under 700W, takes out flask, leaves standstill crystallization; The gained solid phase prod washs with acetonitrile, is being lower than then-0.05MPa, under the condition of 50-100 ℃ vacuum-drying 5-15 hour, specifically can be under-0.08MPa, 70 ℃ condition dry 6 hours; The X-ray diffracting spectrum of product as shown in Figure 2.As seen from the figure, this product is pentacoordinate body silicoorganic compound (sodium salt).
Embodiment 3:
The serpentine that takes by weighing 10g, granularity＜76 μ m is carried the magnesium residue in flask, and the lithium hydroxide of stoichiometric ratios such as adding and 45-90mL ethylene glycol are specifically as follows 60mL; Mixing is placed in the microwave oven, and distillation reaction is 30 minutes under 700W, takes out flask, leaves standstill crystallization; The gained solid phase prod washs with acetonitrile, is being lower than then-0.05MPa, under the condition of 50-100 ℃ vacuum-drying 5-15 hour, specifically can be under-0.08MPa, 70 ℃ condition dry 6 hours; The X-ray diffracting spectrum of product as shown in Figure 3.As seen from the figure, this product is pentacoordinate body silicoorganic compound (lithium salts).
Embodiment 4:
The precipitated silica that takes by weighing 10g, granularity＜76 μ m is in flask, and the barium oxide of stoichiometric ratios such as adding and 45-90mL ethylene glycol are specifically as follows 50mL; Mixing is placed in the microwave oven, and distillation reaction is 12 minutes under 700W, takes out flask, leaves standstill crystallization; The gained solid phase prod washs with acetonitrile, is being lower than then-0.05MPa, under the condition of 50-100 ℃ vacuum-drying 5-15 hour, specifically can be under-0.06MPa, 80 ℃ condition dry 5 hours; The X-ray diffracting spectrum of product as shown in Figure 4.As seen from the figure, this product is sexadentate silicoorganic compound (barium salts).
Embodiment 5:
The wilkinite residue of aluminum-extracted that takes by weighing 10g, granularity＜76 μ m is in flask, and the barium oxide of stoichiometric ratios such as adding and 45-90mL ethylene glycol are specifically as follows 50mL; Mixing is placed in the microwave oven, and distillation reaction is 15 minutes under 700W, takes out flask, leaves standstill crystallization; The gained solid phase prod washs with acetonitrile, is being lower than then-0.05MPa, under the condition of 50-100 ℃ vacuum-drying 5-15 hour, specifically can be under-0.06MPa, 80 ℃ condition dry 5 hours; The X-ray diffracting spectrum of product as shown in Figure 5.As seen from the figure, this product is sexadentate silicoorganic compound (barium salts).
Embodiment six:
Taking by weighing the 10g serpentine carries magnesium residue (granularity＜76 μ m) in flask, the calcium oxide of stoichiometric ratios such as adding and 45-90mL ethylene glycol is specifically as follows 60mL; Mixing is placed in the microwave oven, and distillation reaction is 30 minutes under 700W, takes out flask, leaves standstill crystallization; The gained solid phase prod washs with acetonitrile, is being lower than then-0.05MPa, under the condition of 50-100 ℃ vacuum-drying 5-15 hour, specifically can be under-0.06MPa, 80 ℃ condition dry 5 hours; The X-ray diffracting spectrum of product as shown in Figure 6.As seen from the figure, this product is sexadentate silicoorganic compound (calcium salts).
Remove this part, the residue that extracts behind metal ion with other nonmetalliferous ore of wilkinite, serpentine structural similitude also is a soft silica because of its major ingredient, and high reaction activity and high is arranged too, therefore, can be used for preparing silicoorganic compound by the inventive method equally.
In the distillation reaction in the various embodiments described above, owing to adopt the type of heating of microwave exposure, thereby significantly accelerated speed of response, shortened the reaction times.
Claims (7)
1, a kind of method for preparing silicoorganic compound by soft silica, it is characterized in that with precipitated silica or with the soft silica being that the nonmetalliferous ore of major ingredient extracts residue behind the metal ion as silicon-containing material, in alkali metal hydroxide medium or alkaline earth metal oxide medium, silicon-containing material and adjacent glycol generate silicoorganic compound by distillation reaction.
2, according to claim 1ly prepare the method for silicoorganic compound, it is characterized in that described residue is that wilkinite residue of aluminum-extracted or serpentine are carried the magnesium residue by soft silica.
3, the method for preparing silicoorganic compound by soft silica according to claim 1, it is characterized in that in the 10g precipitated silica of granularity＜76 μ m the sodium hydroxide of stoichiometric ratios such as adding or potassium hydroxide or lithium hydroxide and 45-90mL ethylene glycol; Mixing, distillation reaction, leave standstill crystallization gained solid phase prod and wash, get pentacoordinate body silicoorganic compound through vacuum-drying with acetonitrile.
4, the method for preparing silicoorganic compound by soft silica according to claim 1, it is characterized in that carrying in the magnesium residue sodium hydroxide of stoichiometric ratios such as adding or potassium hydroxide or lithium hydroxide and 45-90mL ethylene glycol at 10g wilkinite residue of aluminum-extracted or the serpentine of granularity＜76 μ m; Mixing, distillation reaction, leave standstill crystallization gained solid phase prod and wash, get pentacoordinate body silicoorganic compound through vacuum-drying with acetonitrile.
5, according to claim 1ly prepare the method for silicoorganic compound, it is characterized in that in the 10g precipitated silica of granularity＜76 μ m the barium oxide of stoichiometric ratios such as adding or calcium oxide and 45-90mL ethylene glycol by soft silica; Mixing, distillation reaction, leave standstill crystallization gained solid phase prod and wash with acetonitrile, vacuum-drying gets the sexadentate silicoorganic compound.
6, the method for preparing silicoorganic compound by soft silica according to claim 1, it is characterized in that carrying in the magnesium residue barium oxide of stoichiometric ratios such as adding or calcium oxide and 45-90mL ethylene glycol at 10g wilkinite residue of aluminum-extracted or the serpentine of granularity＜76 μ m; Mixing, distillation reaction, leave standstill crystallization gained solid phase prod and wash with acetonitrile, vacuum-drying gets the sexadentate silicoorganic compound.
7, describedly prepare the method for silicoorganic compound according to claim 1 or 2 or 3 or 4 or 5 or 6, it is characterized in that in described distillation reaction, adopt the type of heating of microwave exposure by soft silica.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03135078XA CN100425613C (en) | 2003-09-27 | 2003-09-27 | Method for preparing organic silicon compound from amorphous silica |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03135078XA CN100425613C (en) | 2003-09-27 | 2003-09-27 | Method for preparing organic silicon compound from amorphous silica |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1600786A true CN1600786A (en) | 2005-03-30 |
| CN100425613C CN100425613C (en) | 2008-10-15 |
Family
ID=34659200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB03135078XA Expired - Fee Related CN100425613C (en) | 2003-09-27 | 2003-09-27 | Method for preparing organic silicon compound from amorphous silica |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100425613C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618932A (en) * | 2012-03-31 | 2012-08-01 | 合肥工业大学 | Method for preparing basic ammonium aluminum carbonate hydroxide whisker and aluminum oxide whisker co-production liquid sodium silicate from bentonite |
| CN110564380A (en) * | 2019-09-28 | 2019-12-13 | 中国石油集团川庆钻探工程有限公司钻井液技术服务公司 | Inhibitor for drilling fluid and preparation method thereof |
| CN111100155A (en) * | 2019-06-03 | 2020-05-05 | 杭州师范大学 | Is made of SiO2Synthesis method for directly preparing four-coordination siloxane and five-coordination siloxane |
-
2003
- 2003-09-27 CN CNB03135078XA patent/CN100425613C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618932A (en) * | 2012-03-31 | 2012-08-01 | 合肥工业大学 | Method for preparing basic ammonium aluminum carbonate hydroxide whisker and aluminum oxide whisker co-production liquid sodium silicate from bentonite |
| CN102618932B (en) * | 2012-03-31 | 2015-03-25 | 合肥工业大学 | Method for preparing basic ammonium aluminum carbonate hydroxide whisker and aluminum oxide whisker co-production liquid sodium silicate from bentonite |
| CN111100155A (en) * | 2019-06-03 | 2020-05-05 | 杭州师范大学 | Is made of SiO2Synthesis method for directly preparing four-coordination siloxane and five-coordination siloxane |
| CN111100155B (en) * | 2019-06-03 | 2022-11-01 | 杭州师范大学 | Is prepared from SiO2Synthesis method for directly preparing four-coordination siloxane and five-coordination siloxane |
| CN110564380A (en) * | 2019-09-28 | 2019-12-13 | 中国石油集团川庆钻探工程有限公司钻井液技术服务公司 | Inhibitor for drilling fluid and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100425613C (en) | 2008-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| MacKenzie et al. | Formation of aluminosilicate geopolymers from 1: 1 layer-lattice minerals pre-treated by various methods: a comparative study | |
| EP1208105B1 (en) | Process for the formation of polyhedral oligomeric silsesquioxanes | |
| Yanagisawa et al. | Organic derivatives of layered polysilicates: I. Trimethylsilylation of magadiite and kenyaite | |
| JPH07228588A (en) | Production of sulfur containing organic silicon compound | |
| CN1156149A (en) | Di(silyl alkyl) dithioalkane producing method | |
| JPH0463879B2 (en) | ||
| EP0731102B1 (en) | Cyclic phenol sulfide and process for producing the same | |
| CN1020893C (en) | Improved process for preparing vinyl ethers | |
| CN1600786A (en) | Method for preparing organic silicon compound from amorphous silica | |
| JP2001114786A (en) | Method for producing tetraorganooxysilane | |
| JP2009263316A (en) | Method for producing incompletely condensed oligosilsesquioxane | |
| CN1333209A (en) | Process for preparing organic silyl alkyl multisurfide | |
| JP2898754B2 (en) | Method for producing resorcinol | |
| Panasenko et al. | Silicon complexes from rice husk: synthesis, crystal structure, and properties of 1, 2-bis-silatranyloxyethane | |
| JPS6172614A (en) | Production of silicon hydride | |
| JPS6158819A (en) | Manufacture of silica glass powdery and granular particle | |
| KR101699262B1 (en) | Manufacturing Method of Alpha-Arbutin | |
| JP2844767B2 (en) | Method for producing tetrabromobisphenol A | |
| JPS636545B2 (en) | ||
| Mička et al. | Preparation of potassium selenites, their solubility and bonding conditions | |
| JP2811851B2 (en) | Method for producing tetrabromobisphenol A | |
| SU471302A1 (en) | The method of producing borates of alkaline earth and alkali metals | |
| JP2874276B2 (en) | Method for producing high quality tetrabromobisphenol A | |
| Baimbridge et al. | 1-S-(or Se)-dimethylstibino-derivatives of 1-thio-and 1-seleno-β-D-glucopyranose | |
| RU2102325C1 (en) | Method for producing molybdates of alkaline-earth metals |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081015 Termination date: 20120927 |