CN100491384C - Method for synthesizing silane coupler - Google Patents
Method for synthesizing silane coupler Download PDFInfo
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- CN100491384C CN100491384C CNB2005100619667A CN200510061966A CN100491384C CN 100491384 C CN100491384 C CN 100491384C CN B2005100619667 A CNB2005100619667 A CN B2005100619667A CN 200510061966 A CN200510061966 A CN 200510061966A CN 100491384 C CN100491384 C CN 100491384C
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- iodine
- magnesium
- tetraalkoxysilane
- silane coupler
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Abstract
The invention discloses a method for synthesizing silane coupling agent, comprising: feeding the pretreated tetraalkoxy silane 1.5-2.0 mol, magnesium 1.0-1.2 mol and initiating agent iodine 0.001-0.01 mol in the reactor, stirring and heating up; adding pretreated the first haloalkane 1 mol when the temperature is 150-180 Deg C, then cooling to 120-150 Deg C for continuous reaction for 2-5 hours; filtering the generated magnesium salt, distilling the filtering medium to remove dissolvent and initiating agent iodine; fractionating and purifying the got coarse product and getting the silane coupling agent with purity larger than 99%-alkyltrialkoxy silane; the reaction is carried out under protection of nitrogen. The process is characterized by the no usage of ethers solvant which is inflammable and high toxic, simple process, easy-to-control and operate, 95% of productivity and above 99% of purity. The unreacted raw material distilled out can be recovered for reuse.
Description
Technical field
The present invention relates to the synthetic technology of organosilane monomer, specifically relate to a kind of method of synthesizing silane coupler.
Background technology
Silane coupling agent is in materials science field, especially polymer-based composite aspect, has widespread use, for example, it is a kind of effective polymer modification agent, can be used for handling the surface of the wild phase of matrix material, improve the interface performance of matrix material, improve the over-all properties of material.Simultaneously, it also is a kind of important chemical intermediate, can be used for synthetic multiple novel organosilicon compounds.The most noticeable to be exactly by the silane with trifunctional in this class coupling agent is starting raw material, can obtain the silsesquioxane of cage modle, different structure such as trapezoidal by suitable hydrolysis condensation reaction.The silesquioxane compound that obtains can be used as additive (linking agent, thermal characteristics properties-correcting agent, viscosity modifier), functional high molecule material (medical macromolecular materials, photoelectric material), advanced resin matrix (tackiness agent), catalyzer etc. have extensively and important use.
Silane coupling agent with trifunctional is meant that mainly molecular formula can be expressed as RSiX
3Or RSi (OR ')
3Organosilane monomer, wherein R is an organic group, X is an alkoxy or halogen.At present, the method for synthetic coupling agent mainly contains three kinds of direct method, Grignard reagent method and hydrosilation reaction methods.
A. traditional direct method
B.Grignard reagent method
C. hydrosilation reaction
A, R is an organic group among the b; R among the c
1Be unsaturated hydrocarbons, R
2Be corresponding stable hydrocarbon; X is a halogen.
As catalyzer, the shortcoming of existence is temperature of reaction height, separation difficulty (product is a mixture that contains multiple material) to the tradition direct method with copper.Grignard reagent method is with magnesium and SiX
4Join earlier in the solvent, required organic halogen is joined in this solution finish reaction again, the weak point of this method is, halo cycloalkanes and Grignard reagent react difficulty, and product is similarly a mixture, separation difficulty.In addition, the reaction solvent for use is a tetrahydrofuran (THF), and it contacts the back and is very easy to generate the superoxide with intense explosion with air, bring certain danger to operation.The hydrosilation reaction method adopts silicon hydride and the addition reaction of ethylenic unsaturation hydro carbons, and the advantage of this method is that by product is less relatively, but shortcoming is also a lot, as HSiCl
3High volatility, toxicity height, to the equipment requirements harshness, not easy to operate; React required catalyzer (H
2PtCl
66H
2O) cost an arm and a leg (186 yuan/g), and catalytic effect is not satisfactory.
Summary of the invention
The object of the present invention is to provide a kind of method of synthesizing silane coupler.
For achieving the above object, the technical solution used in the present invention is that the step of this method is as follows:
1) tetraalkoxysilane, a halogenated alkane and iodine are used the Calcium Chloride Powder Anhydrous drying respectively, obtain pretreated tetraalkoxysilane, a halohydrocarbon and iodine;
2) embathe the magnesium powder with acetone, with degreasing, incline acetone after, embathed 5～10 minutes with 1～2% hydrochloric acid again, leach magnesium after, more once, it is done soon with washing with alcohol, standby;
Tetraalkoxysilane 1.5～the 2.0mol that 3) will anticipate, magnesium 1.0～1.2mol and initiator iodine 0.001～0.01mol put into reactor, stir and intensification;
4) when temperature rises to 150～180 ℃, add a halogenated alkane 1mol who had anticipated, then be cooled to 120～150 ℃ and continue reaction 2～5h down;
5) filter out the magnesium salts of generation, distillating filtering liquid obtains crude product to steam solvent and initiator iodine;
6) crude product is carried out rectification and purification, obtain purity greater than 99% silane coupling agent---alkyltrialkoxysilaneand;
7) be reflected at more than under the nitrogen protection and carry out.
The mode of the halohydrocarbon that described adding had been anticipated is to be added dropwise to mode.
Described tetraalkoxysilane is tetraethoxysilane or tetramethoxy-silicane.
Alkane in the described halogenated alkane is aliphatic hydrocarbon or aromatic hydrocarbon, and a halo is a chloro or a bromo.
The present invention compares the beneficial effect that has with background technology:
1, adopts the excessive method of tetraalkoxysilane, make solvent, avoided using volatile, inflammable noxious solvents such as ethers, tetrahydrofuran (THF), reduced pollution, improved security with excessive tetraalkoxysilane;
2, adopting the bigger magnesium powder of specific surface area is raw material, has high reaction activity and high and short initiation time;
3, adopt a halogenated alkane dropwise to join method in the suspension of tetraalkoxysilane and magnesium, reduced the generation of side reaction, temperature of reaction can be maintained between 120-150 ℃ steadily carry out;
4, adopt filtration magnesium salts earlier, again to filtrate distillatory method, make the separation purification process of product simpler, easy to operation, and products therefrom has high yield (greater than 95%) and high purity (greater than 99%).In addition, the unreacted raw material that steams can reclaim and reuse.
Embodiment
Embodiment 1: cyclohexyl triethoxyl silane synthetic
Tetraethoxysilane, chlorocyclohexane and iodine carry out drying treatment with Calcium Chloride Powder Anhydrous, and is standby; The magnesium powder embathes degreasing with acetone, inclines to acetone, embathes 5-10 minute with 1～2% hydrochloric acid again, leach magnesium after, more once with washing with alcohol, fast doing, standby.
In the 1000ml there-necked flask, add 416 (2mol) tetraethoxysilane, 24g (1.2mol) magnesium and 2g (0.01mol) iodine, under nitrogen protection, stir (about 100r/min) and intensification.When temperature reached 151 ± 1 ℃, beginning dropwise splashed into 118.5g (1.0mol) chlorocyclohexane, and about 1.5h dropwises.Continue down to finish reaction behind the reaction 2h in 150 ± 1 ℃ more subsequently.Filter out the magnesium salts of generation, filtered liquid is poured into steamed tetraethoxysilane and iodine in the matrass, obtain the crude product of cyclohexyl triethoxyl silane.Again crude product is carried out rectification and purification, promptly obtain productive rate 98%, the water white transparency cyclohexyl triethoxyl silane of purity 99.7% (boiling point is 253 ℃).
Embodiment 2: cyclohexyl triethoxyl silane synthetic
Press the method pre-treatment starting material of embodiment 1, standby.
In the 1000ml there-necked flask, add 312g (1.5mol) tetraethoxysilane, 28.8g (1.2mol) magnesium and 0.2g (0.001mol) iodine.Under nitrogen protection, stir (about 100r/min) and intensification.When temperature reached 180 ± 1 ℃, beginning dropwise splashed into 118.5g (1.0mol) chlorocyclohexane, and about 1.5h dropwises.Continue down to finish reaction behind the reaction 5h in 120 ± 1 ℃ more subsequently.Filter out the magnesium salts of generation, filtered liquid is poured into steamed tetraethoxysilane and iodine in the matrass, obtain the crude product of cyclohexyl triethoxyl silane.Again crude product is carried out rectification and purification, promptly obtain productive rate 97%, the water white transparency cyclohexyl triethoxyl silane of purity 99.5% (boiling point is 253 ℃).
Embodiment 3: cyclopentyl triethoxyl silane synthetic
Press the method pre-treatment starting material of embodiment 1, standby.
In the 1000ml there-necked flask, add 312g (1.5mol) tetraethoxysilane, 26.4g (1.1mol) magnesium and 0.2g (0.001mol) iodine.Under nitrogen protection, stir (about 100r/min) and intensification.When temperature reached 165 ± 1 ℃, beginning dropwise splashed into 105g (1.0mol) chlorocyclopentane, and about 1.5h dropwises.
About 1.5h dropwises.Continue down to finish reaction behind the reaction 3.5h in 130 ± 1 ℃ more subsequently.Filter out the magnesium salts of generation, filtered liquid is poured into steamed tetraethoxysilane and iodine in the matrass, obtain the crude product of cyclohexyl triethoxyl silane.Again crude product is carried out rectification and purification, promptly obtain productive rate 96%, the water white transparency cyclohexyl triethoxyl silane of purity 99.3% (boiling point is 230 ℃).
Embodiment 4: phenyltrimethoxysila,e synthetic
Press the method pre-treatment starting material of embodiment 1, standby.
In the 1000ml there-necked flask, add 273.6g (1.8mol) tetramethoxy-silicane, 28.8g (1.2mol) magnesium and 0.2g (0.001mol) iodine.Under nitrogen protection, stir (about 100r/min) and intensification.When temperature reached 170 ± 1 ℃, beginning dropwise splashed into 105g (1.0mol) bromobenzene, and about 1.5h dropwises.Continue down to finish reaction behind the reaction 3.5h in 140 ± 1 ℃ more subsequently.Filter out the magnesium salts of generation, filtered liquid is poured into steamed tetraethoxysilane and iodine in the matrass, obtain the crude product of cyclohexyl triethoxyl silane.Again crude product is carried out rectification and purification, promptly obtain productive rate 97%, the water white transparency cyclohexyl triethoxyl silane of purity 99.4% (boiling point is 211 ℃).
Claims (4)
1, a kind of method of synthesizing silane coupler is characterized in that the step of this method is as follows:
1) tetraalkoxysilane, a halogenated alkane and iodine are used the Calcium Chloride Powder Anhydrous drying respectively, obtain pretreated tetraalkoxysilane, a halohydrocarbon and iodine;
2) embathe the magnesium powder with acetone, with degreasing, incline acetone after, embathed 5～10 minutes with 1～2% hydrochloric acid again, leach magnesium after, more once, it is done soon with washing with alcohol, standby;
Tetraalkoxysilane 1.5～the 2.0mol that 3) will anticipate, magnesium 1.0～1.2mol and initiator iodine 0.001～0.01mol put into reactor, stir and intensification;
4) when temperature rises to 150～180 ℃, add a halogenated alkane 1mol who had anticipated, then be cooled to 120～150 ℃ and continue reaction 2～5h down;
5) filter out the magnesium salts of generation, distillating filtering liquid obtains crude product to steam solvent and initiator iodine;
6) crude product is carried out rectification and purification, obtain purity greater than 99% silane coupling agent---alkyltrialkoxysilaneand;
7) be reflected at more than under the nitrogen protection and carry out.
2, the method for a kind of synthesizing silane coupler according to claim 1 is characterized in that: the mode of the halohydrocarbon that described adding had been anticipated is to be added dropwise to mode.
3, the method for a kind of synthesizing silane coupler according to claim 1 is characterized in that: described tetraalkoxysilane is tetraethoxysilane or tetramethoxy-silicane.
4, the method for a kind of synthesizing silane coupler according to claim 1 is characterized in that: the alkane in the described halogenated alkane is aliphatic hydrocarbon or aromatic hydrocarbon, and a halo is a chloro or a bromo.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100619667A CN100491384C (en) | 2005-12-13 | 2005-12-13 | Method for synthesizing silane coupler |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100619667A CN100491384C (en) | 2005-12-13 | 2005-12-13 | Method for synthesizing silane coupler |
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| CN1789269A CN1789269A (en) | 2006-06-21 |
| CN100491384C true CN100491384C (en) | 2009-05-27 |
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| CNB2005100619667A Expired - Fee Related CN100491384C (en) | 2005-12-13 | 2005-12-13 | Method for synthesizing silane coupler |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101225090B (en) * | 2007-01-15 | 2011-03-23 | 临邑县鲁晶化工有限公司 | Method for directly synthesizing dialkyl dialkoxy silicane by one-step process |
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Non-Patent Citations (2)
| Title |
|---|
| 环戊基三甲氧基硅烷的合成及应用. 许招会等.应用化工，第33卷第5期. 2004 |
| 环戊基三甲氧基硅烷的合成及应用. 许招会等.应用化工，第33卷第5期. 2004 * |
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Granted publication date: 20090527 Termination date: 20111213 |