CN1532200A - One-step synthesizing cyclohexyl methyl dimethoxy silane without solvent - Google Patents
One-step synthesizing cyclohexyl methyl dimethoxy silane without solvent Download PDFInfo
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- CN1532200A CN1532200A CNA031187870A CN03118787A CN1532200A CN 1532200 A CN1532200 A CN 1532200A CN A031187870 A CNA031187870 A CN A031187870A CN 03118787 A CN03118787 A CN 03118787A CN 1532200 A CN1532200 A CN 1532200A
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- cyclohexyl methyl
- magnesium powder
- dimethoxy silane
- methyl dimethoxy
- cyclohexane
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Abstract
The solvent-free one-step process of synthesizing cyclohexyl methyl dimethoxy silane with methyl dimethoxy silane, cyclohexane halide and magnesium powder in the molar ratio of 1 to 1 to 1-1.5 as material includes compounding material; mixing and heating methyl dimethoxy silane, magnesium powder and catalyst in the amount of 0.1-0.5 % of methyl dimethoxy silane under the protection of N2 and through stirring; dropping slowly 5-15 % of cyclohexane halide; refluxing the materials inside the reactor for 30-40 min while maintaining the temperature; dropping the residual cyclohexane halide; maintaining the temperature for one other 30-40 min; and cooling, filtering and rectifying the filtrate to obtain cyclohexyl methyl dimethoxy silane product. The present invention has the advantages of reasonable, simple and practical process, high yield and high conversion rate, etc.
Description
Technical field
The present invention relates to the industrial chemicals field, particularly a kind of solventless one-step method synthesizing cyclohexyl methyl dimethoxysilane.
Background technology
Cyclohexyl methyl dimethoxy silane [C
6H
11CH
3Si (OCH
3)
2], be called for short CMMS, the industrial Dornor-C that claims again.It produces auxiliary agent as polypropylene---electron donor, play important effect aborning, and can improve the degree of isotacticity of polypropylene product.Its synthesis route mainly contains three major types: organic alkali metal method, silicon hydrogen additive process, Grignard reagent method.Wherein, more with Grignard reagent method and silicon hydrogen additive process again, they have all adopted two methods of solvent synthetic.
In the organosilicon chemistry, the status of Grignard reagent synthesis method is very important, for a long time, scholars have gone through organic group and the activity of halogen in grignard reaction on the Siliciumatom, have also studied the influence of structure, solvent, catalyzer and the reaction conditions etc. of Grignard reagent.The Grignard reagent method is RMgI the earliest, uses RMgBr afterwards instead, and the more cheap RMgCl of the price of use is also arranged, but active not as good as the above two.External main patent has the JP06345781 of chemical company of Japanese SHIN-ETSU HANTOTAI (Shinetsu Chem IncCo) and the US4777278 of U.S. Aksu company (Ako America Inc).They all generate Grignard reagent with cycloalkyl haloalkane and reactive magnesium under the existence condition of organic solvent, the Grignard reagent of generation reacted 12 hours with alkyltrialkoxysilaneand at ambient temperature, purity 95%, yield 83%.Domestic Shaoyang used toluene of chemical research is made solvent, and Bengbu Medical College makes solvent with ether.Usually make solvent with ethers, but because of its boiling point is too low, not easy to operate, and quality product and production technique had disadvantageous effect.Increased the sedimental amount of magnesium salts simultaneously, thereby disturbed filter effect and cause the washing difficulty to increase, thus at present popular be to make solvent with toluene.
The preparation principle of Grignard reagent method is undertaken by following reaction formula:
Organoalkoxysilane is during as the raw material of Grignard reagent, can be without solvent, and very responsive, but normal yield is lower to hydrolysis, and be subjected to sterically hindered influence bigger.
Silicon hydrogen additive process needs with active extremely strong platinum catalyst because the first step is crucial, but platinum catalyst price height, is difficult for reclaiming, and cost is higher, has a large amount of hydrogenchloride to produce simultaneously, and treatment process is more.Domestic Shanghai University Of Engineering Science carries out laboratory study, and Jiangxi Normal University has carried out the research and the produced in small quantities of this technology, but does not see written report; External Mitsui oiling company (Mitsui Petrochremical Inc, Ltd) Shen Qing patent JP05310756 they mainly solve the problem that the rapid absorption of hydrogenchloride is handled, simultaneously platinum catalyst is improved, yield reaches 73.4%.
Silicon hydrogen additive process is undertaken by following reaction formula:
In order to improve platinum catalyst, abroad the someone utilizes nickel catalyzator, for industrial production provides possibility.Main representative has the patent EP792688 and Spain (the Istituto GuidoDonegani of Dow corning company (Dow corning Co) application, S.P.A) patents such as Shen Qing EP281425, EP294745, EP289058, they point out with nickel catalyzator, solvent-free, in the Parr reactor, under 1.4Mpa pressure, lead to hydrogen, and be pressurized to 4.8Mpa, product yield 95%.The improvement biggest advantage of above-mentioned technology is the yield height, and raw material is easy to get, cheaply, but produces and severe reaction conditions, and pressure requires high, and danger is bigger.
Summary of the invention
Technical problem to be solved by this invention is: improve the deficiencies in the prior art, a kind of solventless one-step method synthesizing cyclohexyl methyl dimethoxysilane that is suitable for suitability for industrialized production is provided, make the synthesis technique of cyclohexyl methyl dimethoxy silane have that operation is simple, and improve the yield of cyclohexyl methyl dimethoxy silane and the transformation efficiency of methyltrimethoxy silane.
The technical scheme that the present invention solves its technical problem employing is: adopt the solventless one-step method, with methyltrimethoxy silane, cyclohexane halide, magnesium powder is raw material synthesizing cyclohexyl methyl dimethoxysilane, its technical process comprises: with methyltrimethoxy silane, cyclohexane halide, magnesium powder is raw material, by its mol ratio 1: 1: 1～1.5 batchings; At N
2Protection with methyltrimethoxy silane, magnesium powder, catalyst mix, places the reactor heating, stirs down, and catalyst consumption is 1 of used methyltrimethoxy silane weight～5 ‰; Slowly drip cyclohexane halide, the consumption of cyclohexane halide is 5～15% of its gross weight; Insulation makes in the reactor that material is stable to reflux 30～40 minutes; Drip residual cyclohexane halide; Be incubated 30～40 minutes, reaction finishes; Cold filtration, filtrate is slipped through essence, makes cyclohexyl methyl dimethoxy silane product.
The present invention adopts the Grignard that does not add solvent by the improvement of Dui Geshi reaction process, and a step generates cyclohexyl methyl dimethoxy silane.Therefore, compared with prior art, the present invention has following major advantage:
One. flow process is reasonable: because temperature of reaction is lower, and does not introduce other organic solvent, thereby saved middle-chain, operation is simple to make building-up reactions, and product is easy to separate, good reproducibility, industrial production is stable.
They are two years old. and can improve the transformation efficiency of methyltrimethoxy silane, and the yield and the transformation efficiency of cyclohexyl methyl dimethoxy silane are all reached more than 90%.
They are three years old. reduced investment, and machine utilization is little, equipment spatiotemporal efficiency height, the engineering scale effect is less.
They are four years old. and starting material are inexpensive, are easy to get.
Embodiment
The invention will be further described below in conjunction with embodiment.
The present invention is a basic raw material with methyltrimethoxy silane, cyclohexane halide, magnesium powder, adopts the solventless one-step method, the synthesizing cyclohexyl methyl dimethoxysilane.
One. technical process
Comprise the steps:
A. be raw material with methyltrimethoxy silane, cyclohexane halide, magnesium powder, by its mol ratio 1: 1: 1～1.5 batchings (referring to subordinate list).
B. at N
2Protection with methyltrimethoxy silane, magnesium powder, catalyst mix, places the reactor heating, stirs down.
C. slowly drip cyclohexane halide, the consumption of cyclohexane halide is 5～15% of its gross weight.
D. insulation makes in the reactor that material is stable to reflux 30～40 minutes.
E. drip residual cyclohexane halide, all dripped off in 1～2 hour consuming time.
F. be incubated 30～40 minutes.
G. cold filtration, filtrate is slipped through essence, makes cyclohexyl methyl dimethoxy silane product.
Above-mentioned catalyst consumption is 1 of used methyltrimethoxy silane weight～5 ‰.
About 8 hours of total overall reaction time.
Above-mentioned cyclohexane halide can be selected the substituted cyclohexane hydrocarbon of Cl or Br or I for use, and the water content of substituted cyclohexane hydrocarbon is less than or equal to 100mg/kg.
Used magnesium powder can be selected fresh magnesium powder for use; Perhaps select for use through 5% the rare HCl solution washing and the magnesium powder of dry for standby, the purpose of washing is in order to remove the oxide compound on magnesium powder surface.Magnesium powder degree 20～200 orders, content is all more than or equal to 99%.
Can select iodine or iodide or bromide or methoxyl group chlorination magnesium for use, or its mixture, as catalyzer, consumption is 1 of used methyltrimethoxy silane weight～5 ‰.Can suitably add some initiators in the catalyzer, suitable initiator has bromoalkane, alkoxyl group magnesium salts and intensive polar solvent, and as tetrahydrofuran (THF), DMF etc., add-on is 1 of methyltrimethoxy silane weight～5 ‰.
Can select the reactor of materials such as enamel or stainless steel for use, it has reflux exchanger, thermometer, agitator, well heater and balance feeder.
Two. concrete reaction principle
Two. specific examples
Used cyclohexane halide in following each example is all passed through processed.Its dewatering is: at a diameter is 40mm, and length is 300mm, and be equipped with in the glass fixed bed of flange and back up pad at two ends, adds a certain amount of 5A molecular sieve.At N
2Protection down makes cyclohexane halide pass through fixed bed, deviates from the moisture in the raw material, and the timing sampling analysis makes in the raw material moisture be less than or equals 100mg/kg, and sealing is preserved standby.
Example 1.
In having the 250ml glass round-bottomed flask of reflux exchanger, thermometer, agitator, well heater and balance feeder, at N
2Protection adds the fresh magnesium powder of 12 grams down, 56 gram methyltrimethoxy silanes, 5 gram chlorocyclohexanes and 0.2 gram iodine; heating keeps the stable backflow of material; reflux after 30 minutes, begin to drip remaining 41 gram chlorocyclohexanes, utilize the time about 1 hour all to add.Add back insulation 30 minutes, finish reaction.The reaction solution analytical results is that the transformation efficiency of cyclohexyl methyl dimethoxy silane is 90.3% (in silane), and the yield of cyclohexyl methyl dimethoxy silane is 91.4%.
Example 2
In having the 500ml four-hole glass round-bottomed flask of reflux exchanger, thermometer, agitator, well heater and balance feeder, at N
2Protection adds the fresh magnesium powder of 37 grams down, 152 gram methyltrimethoxy silanes; 12 gram chlorocyclohexanes and 0.6 gram potassiumiodide, the stable backflow of heating maintenance material refluxed after 30 minutes; begin to drip remaining 138 gram chlorocyclohexanes, utilize the time about 1.5 hours all to add.Add back insulation 30 minutes, finish reaction.The reaction solution analytical results is that the transformation efficiency of cyclohexyl methyl dimethoxy silane is 89.2% (in silane), and the yield of cyclohexyl methyl dimethoxy silane is 91.5%.
Example 3
Having reflux exchanger, thermometer, agitator is in the 500ml four-hole glass round-bottomed flask of well heater and balance feeder, at N
2Protection down; add the fresh magnesium powder of 37 grams; 152 gram methyltrimethoxy silanes; the mixture (potassiumiodide accounts for 20-60%) of 12 gram chlorocyclohexanes and 0.6 gram iodine and potassiumiodide; heating keeps the stable backflow of material; reflux after 30 minutes, begin to drip remaining 138 gram chlorocyclohexanes, utilize the time about 1.5 hours all to add.Add back insulation 30 minutes, finish reaction.The reaction solution analytical results is that the transformation efficiency of cyclohexyl methyl dimethoxy silane is 91.5% (in silane), and the yield of cyclohexyl methyl dimethoxy silane is 93.1%.
Example 4
Having reflux exchanger, thermometer, agitator is in the 10000ml four-hole glass round-bottomed flask of well heater and balance feeder, at N
2Protection down; add the fresh magnesium powder of 635 grams; 3000 gram methyltrimethoxy silanes; the mixture (potassiumiodide accounts for 20-60%) of 250 gram chlorocyclohexanes and 5 gram iodine and potassiumiodide; heating keeps the stable backflow of material, refluxes after 30 minutes, adds small amount of bromine ethane (1-5 ‰ with the methyltrimethoxy silane amount is advisable); begin to drip remaining 2230 gram chlorocyclohexanes, utilize the time about 1.5 hours all to add.Add back insulation 30 minutes, finish reaction.The reaction solution analytical results is that the transformation efficiency of cyclohexyl methyl dimethoxy silane is 90.8% (in silane), and the yield of cyclohexyl methyl dimethoxy silane is 91.7%.
Example 5
Having reflux exchanger, thermometer, agitator is in the enamel reaction still of the 200L of well heater and balance feeder, at N
2Protection down; add 12 kilograms of fresh magnesium powder; 70 kilograms of methyltrimethoxy silanes; 10 kilograms of chlorocyclohexanes and 100 gram potassiumiodides; heating keeps the stable backflow of material, refluxes after 30 minutes, adds a small amount of methoxyl group chlorination magnesium (1-5 ‰ with the methyltrimethoxy silane amount is advisable); begin to drip remaining 50 kilograms of chlorocyclohexanes, utilize the time about 1.5 hours all to add.Add back insulation 30 minutes, finish reaction.The reaction solution analytical results is that the transformation efficiency of cyclohexyl methyl dimethoxy silane is 92.6% (in silane), and the yield of cyclohexyl methyl dimethoxy silane is 90.1%.
Chlorocyclohexane in the foregoing description can be replaced by bromocyclohexane, iodocyclohexane.
Three. subordinate list
The formulation parameter table
Above-mentioned methyltrimethoxy silane, cyclohexane halide content are all more than or equal to 99%, and water content is less than or equal to 100mg/kg.Raw material and product carry out analyzing and testing with gas-chromatography.
Claims (6)
1. a method of utilizing methyltrimethoxy silane, cyclohexane halide, magnesium powder synthesizing cyclohexyl methyl dimethoxysilane is characterized in that cyclohexyl methyl dimethoxy silane adopts the solventless one-step method synthetic, and its technical process comprises:
A. be raw material with methyltrimethoxy silane, cyclohexane halide, magnesium powder, by its mol ratio 1: 1: 1～1.5 batchings,
B. at N
2Protection with methyltrimethoxy silane, magnesium powder, catalyst mix, places the reactor heating, stirs down,
C. slowly drip cyclohexane halide, the consumption of cyclohexane halide is 5～15% of its gross weight,
D. insulation makes in the reactor that material is stable to reflux 30～40 minutes,
E. drip residual cyclohexane halide,
F. be incubated 30～40 minutes,
G. cold filtration, filtrate is slipped through essence, makes cyclohexyl methyl dimethoxy silane product,
Above-mentioned catalyst consumption is 1 of used methyltrimethoxy silane weight～5 ‰.
2. the method for synthesizing cyclohexyl methyl dimethoxysilane according to claim 1 is characterized in that used cyclohexane halide is the substituted cyclohexane hydrocarbon of Cl or Br or I.
3. the method for synthesizing cyclohexyl methyl dimethoxysilane according to claim 2 is characterized in that used substituted cyclohexane hydrocarbon, and its water content is less than or equal to 100mg/kg.
4. the method for synthesizing cyclohexyl methyl dimethoxysilane according to claim 1 is characterized in that used magnesium powder is fresh magnesium powder, perhaps is through 5% the rare HCl solution washing and the magnesium powder of dry for standby.
5. the method for synthesizing cyclohexyl methyl dimethoxysilane according to claim 1, it is characterized in that catalyzer is iodine or iodide or bromide or methoxyl group chlorination magnesium, or its mixture, its consumption is 1 of used methyltrimethoxy silane weight～5 ‰.
6. the method for synthesizing cyclohexyl methyl dimethoxysilane according to claim 1 is characterized in that used reactor, for having the enamel reaction still or the stainless steel cauldron of reflux exchanger, thermometer, agitator, well heater and balance feeder.
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| CN 03118787 CN1285599C (en) | 2003-03-18 | 2003-03-18 | One-step synthesizing cyclohexyl methyl dimethoxy silane without solvent |
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| CN 03118787 CN1285599C (en) | 2003-03-18 | 2003-03-18 | One-step synthesizing cyclohexyl methyl dimethoxy silane without solvent |
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| CN1285599C CN1285599C (en) | 2006-11-22 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898459A (en) * | 2012-05-16 | 2013-01-30 | 杭州师范大学 | Preparation method of diethyldimethoxysilane |
| CN106831849A (en) * | 2017-01-24 | 2017-06-13 | 广东信翼科技有限公司 | A kind of preparation method containing allyl based polysiloxane |
| CN106831851A (en) * | 2017-01-24 | 2017-06-13 | 广东信翼科技有限公司 | A kind of preparation method of allyl silicane |
| CN109776598A (en) * | 2019-03-04 | 2019-05-21 | 矽时代材料科技股份有限公司 | A kind of preparation method of the base silane containing hexamethylene |
-
2003
- 2003-03-18 CN CN 03118787 patent/CN1285599C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898459A (en) * | 2012-05-16 | 2013-01-30 | 杭州师范大学 | Preparation method of diethyldimethoxysilane |
| CN102898459B (en) * | 2012-05-16 | 2015-04-22 | 杭州师范大学 | Preparation method of diethyldimethoxysilane |
| CN106831849A (en) * | 2017-01-24 | 2017-06-13 | 广东信翼科技有限公司 | A kind of preparation method containing allyl based polysiloxane |
| CN106831851A (en) * | 2017-01-24 | 2017-06-13 | 广东信翼科技有限公司 | A kind of preparation method of allyl silicane |
| CN109776598A (en) * | 2019-03-04 | 2019-05-21 | 矽时代材料科技股份有限公司 | A kind of preparation method of the base silane containing hexamethylene |
| CN109776598B (en) * | 2019-03-04 | 2021-12-03 | 矽时代材料科技股份有限公司 | Preparation method of cyclohexyl-containing silane |
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| CN1285599C (en) | 2006-11-22 |
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