CN117143136A - Tetramethyl silane and preparation method thereof - Google Patents
Tetramethyl silane and preparation method thereof Download PDFInfo
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- CN117143136A CN117143136A CN202311106245.8A CN202311106245A CN117143136A CN 117143136 A CN117143136 A CN 117143136A CN 202311106245 A CN202311106245 A CN 202311106245A CN 117143136 A CN117143136 A CN 117143136A
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- tetramethylsilane
- magnesium chloride
- methyl magnesium
- trimethylchlorosilane
- solution
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- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims abstract description 66
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000005051 trimethylchlorosilane Substances 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 31
- 239000002808 molecular sieve Substances 0.000 claims description 25
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 18
- 238000001179 sorption measurement Methods 0.000 claims description 12
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000000746 purification Methods 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 34
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- -1 for example Chemical compound 0.000 description 6
- 238000010791 quenching Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012432 intermediate storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XYLXXNFYVQYJRZ-UHFFFAOYSA-M [Cl-].[Mg+]C.C1CCOC1 Chemical compound [Cl-].[Mg+]C.C1CCOC1 XYLXXNFYVQYJRZ-UHFFFAOYSA-M 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical group C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- FOTXAJDDGPYIFU-UHFFFAOYSA-N ethylcyclopropane Chemical compound CCC1CC1 FOTXAJDDGPYIFU-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- 239000005048 methyldichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses tetramethylsilane and a preparation method thereof, wherein the preparation method of tetramethylsilane comprises the following steps: and mixing methyl magnesium chloride and trimethylchlorosilane for reaction, and purifying to obtain the tetramethylsilane. The preparation method of the tetramethylsilane can prepare the tetramethylsilane by selecting the trimethylchlorosilane to react with the methyl magnesium chloride, has simple purification process in the preparation process, is easy to obtain high-purity tetramethylsilane, and can be applied to a standard mass production process.
Description
Technical Field
The invention relates to the technical field of fine chemical synthesis, in particular to tetramethylsilane and a preparation method thereof.
Background
In the traditional process, the current synthesis of 4MS is obtained by enriching and purifying methyl chlorosilane byproducts synthesized by a direct method through methyl chloride and silicon powder under the catalysis of copper. In the formation process, the main product is dimethyl dichlorosilane, which accounts for more than 80 percent of the total amount, and simultaneously, a large amount of methyl chlorosilane mixture is generated, including methyl trichlorosilane, trimethyl chlorosilane, methyl dichlorosilane, low-boiling-point silane mixture (short for low-boiling-point substances, LBR), high-boiling-point silane mixture (short for high-boiling-point substances, HBR) and the like. The low-boiling-point substances contain about 40% of 4MS after enrichment, and the method for enriching and purifying the low-boiling-point substances from the low-boiling-point mixture constitutes the main preparation method of the 4MS at present. The method has higher economic value, and if the purification method is adopted for enrichment and purification, the low-boiling-point substance dangerous waste discharge of enterprises can be effectively reduced, and the enterprise benefit can be increased. However, the method has the advantages that the impurity generated by synthesis is more, the impurity isopentane (30 ℃) with the boiling point (26-28 ℃) similar to that of the target product 4MS exists, and in the rectification process, the 4MS and organic impurities such as isopentane, 2-pentene, cyclopropylethane and the like are observed to have an azeotropic phenomenon, so that the purification difficulty is high.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to provide a preparation method of tetramethylsilane, which can provide a novel preparation method of tetramethylsilane, and the purification process in the preparation process is easier, so that the preparation method can meet the requirement of large-scale industrial production.
In order to achieve the above object, the embodiment of the present invention provides a preparation method of tetramethylsilane, comprising the steps of:
and mixing methyl magnesium chloride and trimethylchlorosilane for reaction, and purifying to obtain the tetramethylsilane.
In one or more embodiments of the present invention, the step of uniformly mixing the methylmagnesium chloride with the trimethylchlorosilane includes:
and in the atmosphere of protective gas, dropwise adding the methyl magnesium chloride solution into the trimethylchlorosilane, and stirring and mixing uniformly.
In one or more embodiments of the present invention, the step of dropping the methyl magnesium chloride solution to the trimethylchlorosilane includes:
dropwise adding a methyl magnesium chloride solution with the temperature of minus 10 ℃ to 0 ℃ into trimethylchlorosilane in an atmosphere with the temperature of not more than 0 ℃.
In one or more embodiments of the invention, the methyl magnesium chloride solution is a diethoxymethane solution of methyl magnesium chloride.
In one or more embodiments of the present invention, the step of mixing and reacting methyl magnesium chloride with trimethylchlorosilane further comprises:
after the methyl magnesium chloride solution is added dropwise, the mixture is heated to 80 to 100 ℃ and reacts for 2 to 3 hours.
In one or more embodiments of the invention, the step of purifying comprises:
and distilling the mixture obtained after the reaction to obtain a crude tetramethylsilane product.
In one or more embodiments of the invention, the step of purifying further comprises:
and (3) carrying out adsorption treatment on the crude tetramethylsilane product by using a molecular sieve.
In one or more embodiments of the invention, the molecular sieve comprises at least one of a 13X molecular sieve and a ZSM-5 molecular sieve.
In one or more embodiments of the invention, the step of purifying further comprises:
and rectifying the crude tetramethylsilane product after the adsorption treatment.
The embodiment of the invention also provides tetramethylsilane, which is prepared by the preparation method of tetramethylsilane.
Compared with the prior art, the preparation method of the tetramethylsilane can prepare the tetramethylsilane by selecting the trimethylchlorosilane to react with the methyl magnesium chloride, has simple purification process in the preparation process, is easy to obtain high-purity tetramethylsilane, and can be applied to a standard mass production process.
Drawings
FIG. 1 is a GC-MS spectrum of tetramethylsilane produced by a process for producing tetramethylsilane according to one embodiment of the present invention;
FIG. 2 is a GC-MS spectrum of crude tetramethylsilane according to one embodiment of the present invention.
Detailed Description
The following detailed description of embodiments of the invention is, therefore, to be taken in conjunction with the accompanying drawings, and it is to be understood that the scope of the invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components.
As shown in fig. 1, a method for preparing tetramethylsilane according to a preferred embodiment of the present invention comprises the steps of:
and mixing methyl magnesium chloride and trimethylchlorosilane for reaction, and purifying to obtain the tetramethylsilane.
It can be understood that the crude product of the tetramethylsilane can be prepared by the reaction of the trimethylchlorosilane and the methyl magnesium chloride, and the tetramethylsilane with high purity can be obtained after purification. Compared with the method for preparing the tetramethylsilane by enrichment and purification from the low-boiling-point mixture in the prior art, the preparation method has the advantages that the purification process is simpler, and the tetramethylsilane with high purity can be obtained by simple purification.
The reaction equation is as follows:
as can be seen from the reaction equation, the molar ratio of methyl magnesium chloride to trimethylchlorosilane is 1:1 preferably, of course, in practice, the amount of methylmagnesium chloride may be somewhat greater to ensure that trimethylchlorosilane is reacted as much as possible to tetramethylsilane.
Specifically, the step of uniformly mixing methyl magnesium chloride and trimethylchlorosilane comprises the following steps: and in the atmosphere of protective gas, dropwise adding the methyl magnesium chloride solution into the trimethylchlorosilane, and stirring and mixing uniformly.
Because methyl magnesium chloride is a format reagent and has high activity, the methyl magnesium chloride is generally prepared into a solution, and is added into trimethylchlorosilane in a dropwise manner to react, so that side reactions are avoided as much as possible.
Wherein, the protective gas plays a role in reducing side reactions. Preferably, the shielding gas may be nitrogen, argon, or the like.
Preferably, the step of dropping the methyl magnesium chloride solution to the trimethylchlorosilane comprises: dropwise adding a methyl magnesium chloride solution with the temperature of minus 10 ℃ to 0 ℃ into trimethylchlorosilane in an atmosphere with the temperature of not more than 0 ℃.
At this temperature, the reaction rate was slower and the methyl magnesium chloride conversion (to tetramethylsilane) was higher.
Preferably, the methyl magnesium chloride solution is a diethoxymethane solution of methyl magnesium chloride. Although the methyl magnesium chloride solution may also be a tetrahydrofuran solution of methyl magnesium chloride. However, tetrahydrofuran and its derivatives are azeotroped with tetramethylsilane, which results in a high difficulty in subsequent purification, and thus, it is preferable to select a diethoxymethane solution of methylmagnesium chloride.
Preferably, the step of mixing and reacting methyl magnesium chloride with trimethylchlorosilane further comprises: after the methyl magnesium chloride solution is added dropwise, the mixture is heated to 80 to 100 ℃ and reacts for 2 to 3 hours.
It will be appreciated that reflux at this temperature ensures that the reaction is complete.
In one embodiment, the step of purifying comprises: and distilling the mixture obtained after the reaction to obtain a crude tetramethylsilane product.
Distillation is mainly used for removing impurities such as magnesium chloride, diethoxymethane and the like in the mixture after the reaction as much as possible, and performing primary purification.
Specifically, the purification step further comprises: and (3) carrying out adsorption treatment on the crude tetramethylsilane by using a molecular sieve. The molecular sieve has the further function of purifying the crude product of the tetramethylsilane.
Preferably, the molecular sieve comprises at least one of a 13X molecular sieve and a ZSM-5 molecular sieve.
In one embodiment, the step of purifying further comprises: and rectifying the crude tetramethylsilane product after the adsorption treatment. The crude tetramethylsilane is further purified by rectification to obtain high purity tetramethylsilane, for example, tetramethylsilane with a product purity of >99.9%.
The embodiment of the invention also provides tetramethylsilane, which is prepared by the preparation method of tetramethylsilane.
The preparation method of tetramethylsilane according to the present invention will be described in detail with reference to specific examples.
Example 1
3258g (30 mol, about 3.84L) of trimethylchlorosilane was charged into a nitrogen-protected reactor and cooled to 0 ℃. Taking 20.1L of methyl magnesium chloride diethoxymethane solution (the concentration is 1.5mol/L, and 30.15mol of methyl magnesium chloride) with the temperature of about-5 ℃ and dropwise adding the solution into a reaction kettle, wherein the temperature is kept at not more than 0 ℃ in the dropwise adding process. After the completion of the dropwise addition, the reaction was stirred and heated to reflux the reaction solution, and the reaction solution was kept at about 100℃for 2 hours. After the reaction, the temperature was lowered to about 45 ℃, the condensed water was closed, distilled, and crude tetramethylsilane was obtained in an intermediate tank, and about 2430g of crude tetramethylsilane was obtained by weighing, and the synthesis yield was about 91.8%. And adding 3L of saturated magnesium chloride aqueous solution into the residual mixture in the reaction kettle to quench unreacted methyl magnesium chloride, filtering to obtain magnesium chloride salt solid, and obtaining filtrate which is diethoxymethane aqueous solution.
The crude tetramethylsilane accumulated in the intermediate tank enters an adsorption column filled with 80wt% of 13X molecular sieve and 20wt% of ZSM-5 molecular sieve through a reboiler, then enters a single-tower rectification process, is extracted from the upper part of the column, and finally obtains 2187g of tetramethylsilane with the final yield of 82.6%, and the purity of the tetramethylsilane is over 99% through GC-MS analysis as shown in figure 1.
Example 2
5430g (50 mol, about 6.40L) of trimethylchlorosilane were charged into a nitrogen-protected reactor and cooled to 0 ℃. Taking 33.5L of methyl magnesium chloride diethoxymethane solution (the concentration is 1.5mol/L, and 50.25mol of methyl magnesium chloride) with the temperature of about-5 ℃ and dropwise adding the solution into a reaction kettle, wherein the temperature is kept at not more than 0 ℃. After the completion of the dropwise addition, the reaction was carried out for 2 hours without heating and stirring. After the reaction, the condensed water was closed, distilled, and crude tetramethylsilane was obtained in an intermediate tank, and weighed to obtain about 1500g of crude tetramethylsilane with a synthetic yield of about 34.0%. And adding 5L of saturated magnesium chloride aqueous solution into the residual mixture in the reaction kettle to quench unreacted methyl magnesium chloride, filtering to obtain magnesium chloride salt solid, and obtaining filtrate which is diethoxymethane aqueous solution.
The crude tetramethylsilane accumulated in the intermediate tank was fed into an adsorption column filled with 80wt%13X molecular sieve and 20wt% ZSM-5 molecular sieve through a reboiler, and fed into a single column rectification process, and extracted from the upper part of the column to obtain 1395g of tetramethylsilane, the final yield of which was 31.6%, and the purity of the tetramethylsilane obtained by GC-MS analysis was substantially the same as that of example 1.
Example 3
3258g (30 mol, about 3.84L) of trimethylchlorosilane was charged into a nitrogen-protected reactor and cooled to 0 ℃. Taking 20.1L of methyl magnesium chloride tetrahydrofuran solution (the concentration is 1.5mol/L, and 30.15mol of methyl magnesium chloride) with the temperature of about-5 ℃ and dropwise adding the solution into a reaction kettle, wherein the temperature is kept to be not more than 0 ℃ in the dropwise adding process. After the completion of the dropwise addition, the reaction was stirred and heated to reflux the reaction solution, and the reaction solution was kept at about 100℃for 2 hours. After the reaction, the temperature was reduced to about 45 ℃, the condensed water was closed, distilled, and crude tetramethylsilane was obtained in an intermediate tank, and about 4800g of crude tetramethylsilane was obtained by weighing, and the synthesis yield was about 181.3% (which indicates that more tetrahydrofuran was contained therein, and the correlation spectrum is shown in FIG. 2). Adding 3L of saturated magnesium chloride aqueous solution into the residual mixture in the reaction kettle to quench unreacted methyl magnesium chloride, filtering to obtain magnesium chloride salt solid, and obtaining filtrate which is tetrahydrofuran aqueous solution.
The crude tetramethylsilane accumulated in the intermediate tank enters an adsorption column filled with 80wt% of 13X molecular sieve and 20wt% of ZSM-5 molecular sieve through a reboiler, and then enters a double-tower rectification process, and the crude tetramethylsilane is extracted from the upper part of 2 towers, so that 1005g of tetramethylsilane is obtained, and the comprehensive yield is about 38.0%. The purity of tetramethylsilane obtained by GC-MS analysis was substantially the same as in example 1.
Example 4
3258g (30 mol, about 3.84L) of trimethylchlorosilane were charged into a nitrogen-protected reactor and cooled to 0 ℃. Taking 20.1L of methyl magnesium chloride diethoxymethane solution (the concentration is 1.5mol/L, and 30.15mol of methyl magnesium chloride) with the temperature of about-5 ℃ and dropwise adding the solution into a reaction kettle, wherein the temperature is kept at not more than 0 ℃ in the dropwise adding process. After the completion of the dropwise addition, the reaction was carried out for 24 hours without heating and stirring. After the reaction is finished, the condensed water is closed, distillation is carried out, and crude tetramethylsilane is obtained in an intermediate storage tank, and the crude tetramethylsilane is obtained by weighing about 1080g, and the synthesis yield is about 40.8%. And adding 3L of saturated magnesium chloride aqueous solution into the residual mixture in the reaction kettle to quench unreacted methyl magnesium chloride, filtering to obtain magnesium chloride salt solid, and obtaining filtrate which is diethoxymethane aqueous solution.
The crude tetramethylsilane accumulated in the intermediate tank was fed through a reboiler into an adsorption column filled with 80wt%13X molecular sieve and 20wt% ZSM-5 molecular sieve, and then fed into a single column rectification process, and extracted from the upper part of the column to obtain 994g of tetramethylsilane, the final yield of which was 37.5%, and the purity of the tetramethylsilane obtained by GC-MS analysis was substantially the same as that of example 1.
Example 5
3258g (30 mol, about 3.84L) of trimethylchlorosilane were charged into a nitrogen-protected reactor and cooled to 0 ℃. Taking 20.1L of methyl magnesium chloride diethoxymethane solution (the concentration is 1.5mol/L, and 30.15mol of methyl magnesium chloride) with the temperature of about-5 ℃ and dropwise adding the solution into a reaction kettle, wherein the temperature is kept at not more than 0 ℃ in the dropwise adding process. After the completion of the dropwise addition, the temperature was raised to 80℃and kept for 2 hours. After the reaction, the condensed water was closed, distilled, and crude tetramethylsilane was obtained in an intermediate tank, and the crude tetramethylsilane was weighed to obtain about 1618g of crude tetramethylsilane, and the synthesis yield was about 61.1%. And adding 3L of saturated magnesium chloride aqueous solution into the residual mixture in the reaction kettle to quench unreacted methyl magnesium chloride, filtering to obtain magnesium chloride salt solid, and obtaining filtrate which is diethoxymethane aqueous solution.
The crude tetramethylsilane accumulated in the intermediate tank enters an adsorption column filled with 80wt% of 13X molecular sieve and 20wt% of ZSM-5 molecular sieve through a reboiler, and then enters a single-tower rectification process, and is extracted from the upper part of the column to obtain 1492g of tetramethylsilane, wherein the final yield is 56.3%, and the purity of the tetramethylsilane obtained through GC-MS analysis is basically the same as that of example 1.
Example 6
3258g (30 mol, about 3.84L) of trimethylchlorosilane were charged into a nitrogen-protected reactor and cooled to 0 ℃. Taking 20.1L of methyl magnesium chloride diethoxymethane solution (the concentration is 1.5mol/L, and 30.15mol of methyl magnesium chloride) with the temperature of about-5 ℃ and dropwise adding the solution into a reaction kettle, wherein the temperature is kept at not more than 0 ℃ in the dropwise adding process. After the completion of the dropwise addition, the temperature was raised to slightly visible boiling of the reaction solution, i.e., about 90℃for 2 hours. After the reaction, the condensed water is closed, distilled, and crude tetramethylsilane is obtained in an intermediate storage tank, and the crude tetramethylsilane is weighed to obtain about 2015g of crude tetramethylsilane with a synthetic yield of about 76.1%. And adding 3L of saturated magnesium chloride aqueous solution into the residual mixture in the reaction kettle to quench unreacted methyl magnesium chloride, filtering to obtain magnesium chloride salt solid, and obtaining filtrate which is diethoxymethane aqueous solution.
The crude tetramethylsilane accumulated in the intermediate tank was fed through a reboiler into an adsorption column filled with 80wt%13X molecular sieve and 20wt% ZSM-5 molecular sieve, and then fed into a single column rectification process, and withdrawn from the upper part of the column to obtain 1894g of tetramethylsilane, the final yield of which was 71.5%, and the purity of the tetramethylsilane obtained by GC-MS analysis was substantially the same as that of example 1.
From the above, it can be seen from the above examples that the synthesis yield of example 1 is highest and less than 100%, so that it can be seen that after the methyl magnesium chloride solution is added dropwise to trimethylchlorosilane, the reaction efficiency can be improved by continuing the reaction at a raised temperature, and the final yield of example 1 is also higher, indicating that the side reaction degree is also not high (because part of tetramethylsilane is lost during the purification itself).
The purity of the pure products according to examples 1 to 6 was nearly similar, thus demonstrating that the preparation method of tetramethylsilane of the present invention can obtain tetramethylsilane with high purity.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. The preparation method of the tetramethylsilane is characterized by comprising the following steps of:
and mixing methyl magnesium chloride and trimethylchlorosilane for reaction, and purifying to obtain the tetramethylsilane.
2. The method for preparing tetramethylsilane according to claim 1, wherein said step of mixing and reacting methylmagnesium chloride with trimethylchlorosilane comprises:
and in the atmosphere of protective gas, dropwise adding the methyl magnesium chloride solution into the trimethylchlorosilane, and stirring and mixing uniformly.
3. The method for preparing tetramethylsilane according to claim 2, wherein said step of adding a solution of methylmagnesium chloride dropwise to trimethylchlorosilane comprises:
dropwise adding a methyl magnesium chloride solution with the temperature of minus 10 ℃ to 0 ℃ into trimethylchlorosilane in an atmosphere with the temperature of not more than 0 ℃.
4. The method for preparing tetramethylsilane according to claim 2, wherein said methyl magnesium chloride solution is diethoxymethane solution of methyl magnesium chloride.
5. The method for preparing tetramethylsilane according to claim 4, wherein said step of mixing and reacting methyl magnesium chloride with trimethylchlorosilane further comprises:
after the methyl magnesium chloride solution is added dropwise, the mixture is heated to 80 to 100 ℃ and reacts for 2 to 3 hours.
6. The method of preparing tetramethylsilane according to claim 1, wherein said purifying step comprises:
and distilling the mixture obtained after the reaction to obtain a crude tetramethylsilane product.
7. The method of preparing tetramethylsilane according to claim 6, wherein said purifying step further comprises:
and (3) carrying out adsorption treatment on the crude tetramethylsilane product by using a molecular sieve.
8. The method of preparing tetramethylsilane according to claim 7, wherein said molecular sieve comprises at least one of a 13X molecular sieve and a ZSM-5 molecular sieve.
9. The method of preparing tetramethylsilane according to claim 7, wherein said purifying step further comprises:
and rectifying the crude tetramethylsilane product after the adsorption treatment.
10. A tetramethylsilane produced by the process for producing a tetramethylsilane according to any one of claims 1 to 9.
Priority Applications (1)
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| CN117624214A (en) * | 2024-01-24 | 2024-03-01 | 全椒亚格泰电子新材料科技有限公司 | Preparation method of tetramethylsilane |
| CN117624214B (en) * | 2024-01-24 | 2024-05-17 | 全椒亚格泰电子新材料科技有限公司 | Preparation method of tetramethylsilane |
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