Nothing Special   »   [go: up one dir, main page]

CN115448944A - Synthesis method of methyl phenyl dimethoxy silane - Google Patents

Synthesis method of methyl phenyl dimethoxy silane Download PDF

Info

Publication number
CN115448944A
CN115448944A CN202210951850.4A CN202210951850A CN115448944A CN 115448944 A CN115448944 A CN 115448944A CN 202210951850 A CN202210951850 A CN 202210951850A CN 115448944 A CN115448944 A CN 115448944A
Authority
CN
China
Prior art keywords
parts
solvent
reaction kettle
bromobenzene
grignard
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.)
Pending
Application number
CN202210951850.4A
Other languages
Chinese (zh)
Inventor
李书兵
杜斌
王文金
江晨
沈谦
李海娟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hubei Xingrui Silicon Material Co Ltd
Original Assignee
Hubei Xingrui Silicon Material Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hubei Xingrui Silicon Material Co Ltd filed Critical Hubei Xingrui Silicon Material Co Ltd
Priority to CN202210951850.4A priority Critical patent/CN115448944A/en
Publication of CN115448944A publication Critical patent/CN115448944A/en
Pending legal-status Critical Current

Links

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
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • 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
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)

Abstract

The invention relates to a synthesis method of methyl phenyl dimethoxy silane, which comprises the steps of adding magnesium powder and a proper amount of ether solvent into a Grignard reaction kettle, and dropwise adding bromobenzene to start a Grignard reaction; under the condition of maintaining reflux, adding mixed solution consisting of chlorobenzene, bromobenzene and ether solvent at a constant speed, and cooling by introducing nitrogen gas to obtain a chlorobenzene grignard reagent; adding methyltrimethoxysilane into a synthesis reaction kettle, dropwise adding a Grignard reagent into the synthesis reaction kettle, preserving heat after dropwise adding, adding a second solvent, adding chlorosilane into the synthesis reaction kettle, and preserving heat for reaction; filtering after the reaction is finished, rectifying the filtrate at normal pressure to recover the solvent and the methyltrimethoxysilane, and then rectifying under reduced pressure to obtain the product of the methylphenyl dimethoxysilane. The invention avoids the introduction of impurities such as iodine in the initiation process by adding a small amount of bromobenzene, simultaneously ensures the stability of the preparation process of the Grignard reagent, effectively removes the dissolved salt in the filtrate system by using chlorosilane and a solvent, and improves the recovery rate of the methyltrimethoxysilane.

Description

Synthesis method of methyl phenyl dimethoxy silane
Technical Field
The invention relates to a synthetic method of methyl phenyl dimethoxy silane, belonging to the technical field of organic chemical synthesis.
Background
The methyl phenyl dimethoxy silane is an important organic silicon monomer, can provide a single methyl phenyl silica chain link in the polymerization process, can endow organic silicon materials with more excellent performances such as high and low temperature resistance, electric insulation grade, irradiation resistance and the like, and is commonly used for preparing methyl phenyl silicone oil, silicon rubber and silicon resin. Because the methyl phenyl dimethoxy silane has more active property, the methyl phenyl dimethoxy silane can be used for reactions such as substitution, ester exchange and the like, and can also be used as an organic synthesis intermediate to prepare organic silicon derivatives which have higher alkylation degree, unique structure and excellent performance.
At present, the preparation methods of the methylphenyldimethoxysilane reported in the literature mainly comprise an alcoholysis method, a sodium condensation method and a Grignard method. The alcoholysis method is characterized in that methyl phenyl dichlorosilane is subjected to methanolysis to obtain methyl phenyl dimethoxysilane, the main technical key point of the alcoholysis method is how to effectively remove HCL generated by alcoholysis, the alcoholysis method has high requirements on equipment corrosion resistance, and meanwhile, the alcoholysis method needs a phenyl chlorosilane monomer as a raw material, so that the current market yield of the methyl phenyl dichlorosilane is low, and harmful substances such as polychlorinated biphenyl and the like possibly exist in the methyl phenyl dichlorosilane, and the alcoholysis is carried out after the methyl phenyl dichlorosilane is remained in a system to influence the product quality; the sodium condensation method is to prepare sodium sand by chlorobenzene and sodium in a solvent, and then prepare methyl phenyl dimethoxysilane by reacting with methyl trimethoxy silane, and the main defects of the process are that the storage and transportation of sodium have larger potential safety hazard; the Grignard method is to generate a Grignard reagent by adopting halogenated benzene (bromobenzene or chlorobenzene) and magnesium powder, and the Grignard reagent reacts with methyltrimethoxysilane to obtain the methyl phenyl dimethoxysilane.
The study of the grignard method mainly focuses on the grignard reagent initiation preparation and reaction, but the subsequent separation study of the reaction product is less, for example, CN104017017 introduces that the grignard reaction is carried out by using methyltrimethoxysilane instead of methyltriethoxysilane, so that the selectivity is improved, the grignard reaction is initiated by using an initiator, and the selectivity of the methylphenyldimethoxysilane reaches more than 85 percent, but the subsequent separation process is not involved in the patent, and simultaneously impurities are introduced by adding the initiation catalyst iodine.
CN105732692A adopts methyl trichlorosilane as an accelerator to promote the Grignard reaction, the Grignard reaction is filtered after the reaction is finished, the filter cake is washed by methyl trimethoxysilane, and the yield of the filtrate methyl phenyl dimethoxysilane is 87.5 percent. The methyl trichlorosilane as the promoter mentioned in the patent can react with methoxy magnesium chloride to generate magnesium chloride and methyl trimethoxy silane, but the addition of the promoter is mainly used for promoting the reaction, and needs to be added at the same time of the Grignard reaction, and three problems exist. Firstly, the addition amount is not easy to control, the conversion rate of Grignard reaction fluctuates, the generated methoxyl magnesium chloride fluctuates, meanwhile, the consumption of the methyl trichlorosilane serving as an accelerant and reacting with trace water in a system is not a fixed value, the addition amount is small, the methoxyl magnesium chloride cannot completely react, the addition amount is large, and the methyl trichlorosilane can react with the Grignard reagent to generate the methyl phenyl dichlorosilane. And secondly, the methyl trichlorosilane promoter has higher activity than methyl trimethoxysilane, so that a diphenyl product is more easily generated, and the conversion rate of the methyl phenyl dimethoxy is reduced. Thirdly, the generated salt and the product system can not be effectively separated, although the patent mentions that the yield of the methyl phenyl dimethoxy silane is improved by adopting the methyl trimethoxy silane to wash filter cakes, the loss of the methyl trimethoxy silane is increased.
In the disclosed synthesis process of methyl phenyl dimethoxy grignard method, the following disadvantages exist: the Grignard method has difficult initiation, an initiation catalyst is needed, and the system and the raw materials contain water, so the system and the raw materials can be quenched by a small amount of water even after the initiation is finished and cannot continue to react; 2. after the Grignard reaction is completed, the generated methoxyl magnesium chloride is complexed with methyl trimethoxy silane, and simultaneously, the generated salt can not be effectively precipitated, the methyl trimethoxy silane is not easy to recover during the filtration, and in addition, the methyl trimethoxy silane is adopted to wash the filter cake to improve the yield of the methyl phenyl dimethoxy silane, so the loss of the methyl trimethoxy silane is large; 3. trace alkoxy magnesium chloride is dissolved in the system, and side reaction and solidification are easy to occur when the subsequent rectification temperature is higher.
Disclosure of Invention
In order to solve the problems in the process of preparing the methylphenyldimethoxysilane by the Grignard method, the preparation method of the methylphenyldimethoxysilane is provided.
The preparation method of the methyl phenyl dimethoxy silane is characterized by comprising the following steps:
(1) Adding magnesium powder and a proper amount of ether solvent into a Grignard reaction kettle, dropwise adding bromobenzene, heating up, refluxing and starting the Grignard reaction, wherein the initiation time is 15-30min;
(2) Under the condition of maintaining reflux, adding mixed solution consisting of chlorobenzene, bromobenzene and ether solvent at a constant speed, and cooling by introducing nitrogen gas to obtain a chlorobenzene grignard reagent;
(3) Adding methyltrimethoxysilane into a synthesis reaction kettle, heating to 50-80 ℃, dropwise adding a Grignard reagent into the synthesis reaction kettle, preserving heat after dropwise adding is finished, adding a second solvent, adding chlorosilane into the synthesis reaction kettle, and preserving heat for reaction; filtering after the reaction is finished, rectifying the filtrate at normal pressure to recover the solvent and the methyltrimethoxysilane, and then rectifying under reduced pressure to obtain the product of the methylphenyl dimethoxysilane.
The ether solvent in the step (1) and the ether solvent in the step (2) are tetrahydrofuran or 2-methyltetrahydrofuran.
The amount of bromobenzene for starting the Grignard reaction in the step (1) is 1-5% of the mass of magnesium powder; the temperature of the heating reflux reaction is the boiling point of the ether solvent, more specifically 60-80 ℃.
The raw material feeding amounts in the steps (1), (2) and (3) are 15-35 parts by mass of magnesium powder, 110-150 parts by mass of chlorobenzene, 3.0-20.0 parts by mass of bromobenzene, 70-120 parts by mass of ether solvent and 270-550 parts by mass of methyltrimethoxysilane.
The mass ratio of bromobenzene in step (1) to bromobenzene in step (2) is 0.01-0.1:0.2-1.0; the mass ratio of the ether solvent in the step (1) to the ether solvent in the step (2) is 1:1-5.
The second solvent in the step (3) is a weak polar solvent, and the boiling point of the second solvent is more than 50 ℃; preferred are hydrocarbon solvents having a polarity of less than 2.4 and a boiling point of greater than 50 ℃; more specifically, it comprises toluene (2.4/111 ℃), n-heptane (0.2/98 ℃), cyclohexane (0.1/81 ℃), n-hexane (0.06/69 ℃), and the amount used is 100-150 parts; the dripping time of the mixed solution consisting of chlorobenzene, bromobenzene and ether solvent is 1-2h; the dripping time of the chlorobenzene grignard reagent is 1.5 to 2.5 hours.
The chlorosilane is methyl chlorosilane and monophenyl chlorosilane; specifically, methyl trichlorosilane, dimethyl dichlorosilane, trimethyl monochlorosilane, phenyl trichlorosilane, methyl phenyl dichlorosilane and dimethyl phenyl chlorosilane; preferred are methylphenyldichlorosilane and methyltrichlorosilane.
The end point of chlorosilane addition is that the pH value of the system is 5-7.
The second solvent is a weak polar solvent with a boiling point higher than 50 ℃; preferred are hydrocarbon solvents having a polarity of less than 2.4 and a boiling point of greater than 50 ℃; more specifically, it comprises toluene (2.4/111 ℃), n-heptane (0.2/98 ℃), cyclohexane (0.1/81 ℃), n-hexane (0.06/69 ℃), and the amount used is 100-150 parts; the dropping time of the mixed solution of chlorobenzene, bromobenzene and ether solvent is 1-2h; the dripping time of the chlorobenzene grignard reagent is 1.5 to 2.5 hours.
Compared with the prior art, the invention has the advantages that:
1. bromobenzene is used as a benzene source to initiate the Grignard reaction, no additional initiating catalyst is needed, and no additional impurity is introduced; the Grignard reaction adopts a small amount of mixture of bromobenzene and chlorobenzene as a benzene source to prepare the Grignard reagent, so that trace moisture is prevented from quenching the Grignard reaction, and the preparation process of the Grignard reagent is ensured to be stable.
2. After the Grignard reagent and the methyltrimethoxysilane completely react, adding chlorosilane to neutralize the methoxy magnesium chloride, controlling the neutralization end point through the pH value of the system, effectively controlling the adding amount of the chlorosilane, completely neutralizing the methoxy magnesium chloride, and removing the complexation of the methoxy magnesium chloride, the methyltrimethoxysilane and the methylphenyldimethoxysilane.
3. And a second solvent is added to promote the effective precipitation of magnesium chloride, improve the filtration efficiency and reduce the loss of the methyltrimethoxysilane.
Detailed Description
Example 1
Adding 24 parts of magnesium powder and 36 parts of 2-methyltetrahydrofuran solvent into a Grignard reaction kettle, dropwise adding 0.24 part of bromobenzene, heating to 80 ℃, refluxing to start the Grignard reaction, and initiating for 30min;
under the condition of maintaining reflux, uniformly adding mixed solution consisting of 145 parts of chlorobenzene, 3.2 parts of bromobenzene and 36 parts of solvent 2-methyltetrahydrofuran, dropwise adding for 2 hours, and cooling by introducing nitrogen gas to obtain a chlorobenzene grignard reagent;
272 parts of methyltrimethoxysilane is added into a synthesis reaction kettle, the temperature is raised to 80 ℃, a chlorobenzene grignard reagent is dripped into the synthesis reaction kettle, the temperature is kept after the dripping is finished for 2.5 hours, 150 parts of cyclohexane is added, the methylphenyldichlorosilane is dripped into the synthesis reaction kettle, and the pH is titrated to =5; after the reaction was completed, it was filtered.
MgCl 2 Yield 83.1 parts; the recovery rate of the methyltrimethoxysilane is 117.7 parts, and the recovery rate is 85.6 percent; the yield of the methylphenyldimethoxysilane was 230 parts and 85.2% of the product was obtained.
Rectifying the filtrate, recovering solvent and methyltrimethoxysilane at normal pressure, and rectifying at-0.096 Mpa/115 deg.C to obtain methylphenyl dimethoxysilane with purity of 99.1%; the yield thereof was found to be 92.2%.
Example 2
Adding 24 parts of magnesium powder and 40 parts of tetrahydrofuran solvent into a Grignard reaction kettle, dropwise adding 0.48 part of bromobenzene, heating to 66 ℃, refluxing and starting the Grignard reaction, wherein the initiation time is 25min;
under the condition of maintaining reflux, uniformly adding mixed solution consisting of 135 parts of chlorobenzene, 6.5 parts of bromobenzene and 56 parts of solvent tetrahydrofuran, dropwise adding for 1.5h, and cooling by introducing nitrogen to obtain a chlorobenzene grignard reagent;
adding 362 parts of methyltrimethoxysilane into a synthesis reaction kettle, heating to 75 ℃, dropwise adding a chlorobenzene grignard reagent into the synthesis reaction kettle, preserving heat after dropwise adding is completed for 2 hours, adding 140 parts of n-heptane, dropwise adding methyltrichlorosilane into the synthesis reaction kettle, and titrating to pH =6; after the reaction was completed, it was filtered.
MgCl 2 Yield 84.3 parts; 237.4 parts of methyltrimethoxysilane, 87.2% of recovery, 155.3 parts of methylphenyldimethoxysilane, 86.3% of recovery.
Rectifying the filtrate, recovering solvent and methyl trimethoxy silane at normal pressure, and rectifying at-0.096 Mpa/115 deg.C to obtain methyl phenyl dimethoxy silane with purity of 99.3%; the yield thereof was found to be 91.8%.
Example 3
Adding 24 parts of magnesium powder and 45 parts of tetrahydrofuran solvent into a Grignard reaction kettle, dropwise adding 0.72 part of bromobenzene, heating to 66 ℃, refluxing and starting the Grignard reaction, wherein the initiation time is 20min;
under the condition of maintaining reflux, uniformly adding a mixed solution consisting of 125 parts of chlorobenzene, 9.8 parts of bromobenzene and 75 parts of solvent tetrahydrofuran, dropwise adding for 1.5h, and cooling by introducing nitrogen to obtain a chlorobenzene grignard reagent;
adding 452 parts of methyltrimethoxysilane into a synthesis reaction kettle, heating to 70 ℃, dropwise adding a chlorobenzene grignard reagent into the synthesis reaction kettle, preserving heat after dropwise adding is completed for 2 hours, adding 130 parts of cyclohexane, dropwise adding methyltrichlorosilane into the synthesis reaction kettle, and titrating to pH =5; after the reaction was completed, it was filtered.
MgCl 2 Yield 85.2 parts; 318.1 parts of methyl trimethoxy silane is recovered, and the recovery rate is 87.8 percent; the yield of methylphenyldimethoxysilane was 158.8 parts, and 88.2% is obtained.
Rectifying the filtrate, recovering solvent and methyltrimethoxysilane at normal pressure, and rectifying at-0.096 Mpa/115 deg.C to obtain methylphenyl dimethoxysilane with purity of 99.8%; the yield thereof was found to be 90.6%.
Example 4
Adding 24 parts of magnesium powder and 45 parts of tetrahydrofuran solvent into a Grignard reaction kettle, dropwise adding 0.96 part of bromobenzene, heating to 66 ℃, refluxing and starting the Grignard reaction, wherein the initiation time is 15min;
under the condition of maintaining reflux, uniformly adding a mixed solution consisting of 120 parts of chlorobenzene, 12.5 parts of bromobenzene and 75 parts of solvent tetrahydrofuran, dropwise adding for 1 h, and cooling by introducing nitrogen gas to obtain a chlorobenzene grignard reagent;
adding 542 parts of methyltrimethoxysilane into a synthesis reaction kettle, heating to 65 ℃, dropwise adding a chlorobenzene grignard reagent into the synthesis reaction kettle, keeping the temperature after completing dropwise adding of 1.5h, adding 120 parts of toluene, dropwise adding the methylphenyldichlorosilane into the synthesis reaction kettle, and titrating to pH =7; after the reaction was completed, it was filtered.
MgCl 2 Yield 87.2 parts; the recovery amount of methyltrimethoxysilane was 363.9 parts, the recovery rate was 89.3%, and the recovery amount of methylphenyldimethoxysilane was 240.8 parts, the yield was 89.5%.
Rectifying the filtrate, recovering solvent and methyltrimethoxysilane at normal pressure, and rectifying at-0.096 Mpa/115 deg.C to obtain methylphenyl dimethoxysilane with purity of 99.1%; the yield thereof was found to be 93%.
Example 5
Adding 24 parts of magnesium powder and 45 parts of tetrahydrofuran solvent into a Grignard reaction kettle, dropwise adding 1.2 parts of bromobenzene, heating to 66 ℃, refluxing and starting the Grignard reaction, wherein the initiation time is 15min;
under the condition of maintaining reflux, uniformly adding a mixed solution consisting of 120 parts of chlorobenzene, 15 parts of bromobenzene and 75 parts of solvent tetrahydrofuran, dropwise adding for 1 h, and cooling by introducing nitrogen to obtain a chlorobenzene grignard reagent;
542 parts of methyltrimethoxysilane is added into a synthesis reaction kettle, the temperature is raised to 50 ℃, a chlorobenzene grignard reagent is dripped into the synthesis reaction kettle, the temperature is kept after 1.5h is dripped, 110 parts of toluene is added, methyltrichlorosilane is dripped into the synthesis reaction kettle, and the pH value is titrated to =5; after the reaction was completed, the mixture was filtered.
MgCl 2 Yield 86 parts; the recovery rate of the methyltrimethoxysilane is 400.3, 88.5 percent, and the recovery rate of the methylphenyldimethoxysilane is 160.6 percent, 89.2 percent.
Rectifying the filtrate, recovering solvent and methyl trimethoxy silane at normal pressure, and rectifying at-0.096 Mpa/115 deg.C to obtain methyl phenyl dimethoxy silane with purity of 99.5%; the yield thereof was found to be 91.2%.
Example 6
Adding 24 parts of magnesium powder and 45 parts of tetrahydrofuran solvent into a Grignard reaction kettle, dropwise adding 1.2 parts of bromobenzene, heating to 66 ℃, refluxing and starting the Grignard reaction, wherein the initiation time is 20min;
under the condition of maintaining reflux, uniformly adding mixed solution consisting of 135 parts of chlorobenzene, 15 parts of bromobenzene and 75 parts of solvent tetrahydrofuran, dropwise adding for 1.5h, and cooling by introducing nitrogen gas to obtain a chlorobenzene grignard reagent;
adding 542 parts of methyltrimethoxysilane into a synthesis reaction kettle, heating to 66 ℃, dropwise adding a chlorobenzene grignard reagent into the synthesis reaction kettle, keeping the temperature after completing dropwise adding of 1.5h, adding 150 parts of toluene, dropwise adding methyltrichlorosilane into the synthesis reaction kettle, and titrating to pH =6; after the reaction was completed, it was filtered.
MgCl 2 Yield 89.5 parts; methyl trimethoxy silane recovery amount 406.6 partsThe recovery rate was 89.9%, the yield of methylphenyldimethoxysilane was 162.9 parts, and the yield was 90.5%.
Rectifying the filtrate, recovering solvent and methyl trimethoxy silane at normal pressure, and rectifying at-0.096 Mpa/115 deg.C to obtain methyl phenyl dimethoxy silane with purity of 99.4%; the yield thereof was found to be 91.2%.
Example 7
Adding 24 parts of magnesium powder and 45 parts of tetrahydrofuran solvent into a Grignard reaction kettle, dropwise adding 1.2 parts of bromobenzene, heating to 66 ℃, refluxing and starting the Grignard reaction, wherein the initiation time is 20min;
under the condition of maintaining reflux, uniformly adding a mixed solution consisting of 135 parts of chlorobenzene, 15 parts of bromobenzene and 75 parts of solvent tetrahydrofuran, dropwise adding for 1.5h, and cooling by introducing nitrogen gas to obtain a chlorobenzene grignard reagent;
adding 542 parts of methyltrimethoxysilane into a synthesis reaction kettle, heating to 66 ℃, dropwise adding a chlorobenzene grignard reagent into the synthesis reaction kettle, keeping the temperature after completing dropwise adding of 1.5h, adding 150 parts of normal hexane, dropwise adding methyltrichlorosilane into the synthesis reaction kettle, and titrating to pH =7; after the reaction was completed, the mixture was filtered.
MgCl 2 Yield 85.5 parts; the recovery of methyl trimethoxy silane is 398.9, 89.3%, and the recovery of methyl phenyl dimethoxy silane is 160.7% and 89.3%.
Rectifying the filtrate, recovering solvent and methyltrimethoxysilane at normal pressure, and rectifying at-0.096 Mpa/115 deg.C to obtain methylphenyl dimethoxysilane with purity of 99.2%; the yield thereof was found to be 91.2%.
Example 8
Adding 24 parts of magnesium powder and 40 parts of tetrahydrofuran solvent into a Grignard reaction kettle, dropwise adding 0.48 part of bromobenzene, heating to 66 ℃, refluxing and starting the Grignard reaction, wherein the initiation time is 25min;
under the condition of maintaining reflux, uniformly adding a mixed solution consisting of 135 parts of chlorobenzene, 6.5 parts of bromobenzene and 56 parts of solvent tetrahydrofuran, dropwise adding for 1.5h, and cooling by introducing nitrogen to obtain a chlorobenzene grignard reagent;
adding 362 parts of methyltrimethoxysilane into a synthesis reaction kettle, heating to 75 ℃, dropwise adding a chlorobenzene grignard reagent into the synthesis reaction kettle, preserving heat after dropwise adding is completed for 2 hours, adding 140 parts of n-heptane, dropwise adding trimethylchlorosilane into the synthesis reaction kettle, and titrating to pH =6; after the reaction was completed, it was filtered.
MgCl 2 Yield 84.1 parts; 198 parts of methyltrimethoxysilane, 87.0% and 155.2 parts of methylphenyldimethoxysilane, 86.2% respectively.
Rectifying the filtrate, recovering solvent and methyltrimethoxysilane at normal pressure, and rectifying at-0.096 Mpa/115 deg.C to obtain methylphenyl dimethoxysilane with purity of 99.2%; the yield thereof was found to be 91.5%.
Example 9
Adding 24 parts of magnesium powder and 36 parts of 2-methyltetrahydrofuran solvent into a Grignard reaction kettle, dropwise adding 0.24 part of bromobenzene, heating to 80 ℃, refluxing to start the Grignard reaction, and initiating for 30min;
under the condition of maintaining reflux, uniformly adding mixed solution consisting of 145 parts of chlorobenzene, 3.2 parts of bromobenzene and 36 parts of solvent 2-methyltetrahydrofuran, dropwise adding for 2 hours, and introducing nitrogen for cooling to obtain a chlorobenzene grignard reagent;
272 parts of methyltrimethoxysilane is added into a synthesis reaction kettle, the temperature is raised to 80 ℃, a chlorobenzene grignard reagent is dripped into the synthesis reaction kettle, the temperature is kept after the dripping is finished for 2.5 hours, 150 parts of cyclohexane is added, phenyltrichlorosilane is dripped into the synthesis reaction kettle, and the pH is titrated to =5; after the reaction was completed, it was filtered.
MgCl 2 Yield 83.2 parts; the recovery amount of the methyltrimethoxysilane is 117.3 parts, and the recovery rate is 85.3 percent; the yield of the methyl phenyl dimethoxy silane is 153.2 parts and 85.1 percent.
Rectifying the filtrate, recovering solvent and methyltrimethoxysilane at normal pressure, and rectifying at-0.096 Mpa/115 deg.C to obtain methylphenyl dimethoxysilane with purity of 99.0%; the yield thereof was found to be 91.2%.
Comparative example 1
Adding 24 parts of magnesium powder and 45 parts of tetrahydrofuran solvent into a Grignard reaction kettle, dropwise adding 1.2 parts of bromobenzene, heating to 66 ℃, refluxing and starting the Grignard reaction, wherein the initiation time is 20min;
under the condition of maintaining reflux, uniformly adding a mixed solution consisting of 135 parts of chlorobenzene, 15 parts of bromobenzene and 75 parts of solvent tetrahydrofuran, dropwise adding for 1.5h, and cooling by introducing nitrogen gas to obtain a chlorobenzene grignard reagent;
adding 542 parts of methyltrimethoxysilane into a synthesis reaction kettle, heating to 66 ℃, dropwise adding a chlorobenzene grignard reagent into the synthesis reaction kettle, keeping the temperature after completing dropwise adding of 1.5h, adding 130 parts of tetrahydrofuran, dropwise adding methyltrichlorosilane into the synthesis reaction kettle, and titrating to pH =5; after the reaction was completed, the mixture was filtered.
MgCl 2 Yield 70.4 parts; the recovery rate of the methyltrimethoxysilane is 318.9 parts, 70.5 percent, and the recovery rate of the methylphenyldimethoxysilane is 153 parts and 85 percent.
Rectifying the filtrate, recovering solvent and methyltrimethoxysilane at normal pressure, and rectifying at-0.096 Mpa/115 deg.C to obtain methylphenyl dimethoxysilane with purity of 99.2%; the yield thereof was found to be 80.7%.
Comparative example 2
Adding 24 parts of magnesium powder and 45 parts of tetrahydrofuran solvent into a Grignard reaction kettle, dropwise adding 1.2 parts of bromobenzene, heating to 66 ℃, refluxing and starting the Grignard reaction, wherein the initiation time is 20min;
under the condition of maintaining reflux, uniformly adding a mixed solution consisting of 135 parts of chlorobenzene, 15 parts of bromobenzene and 75 parts of solvent tetrahydrofuran, dropwise adding for 1.5h, and cooling by introducing nitrogen gas to obtain a chlorobenzene grignard reagent;
adding 542 parts of methyltrimethoxysilane into a synthesis reaction kettle, heating to 66 ℃, dropwise adding a chlorobenzene grignard reagent into the synthesis reaction kettle, keeping the temperature after completing dropwise adding of 1.5h, adding 130 parts of acetone, dropwise adding methyltrichlorosilane into the synthesis reaction kettle, and titrating to pH =6; after the reaction was completed, it was filtered.
MgCl 2 Yield 68.2 parts; the recovery rate of the methyltrimethoxysilane is 299.4, the recovery rate is 66.2 percent, the recovery rate of the methylphenyldimethoxysilane is 149.8 parts, and the yield is 83.2 percent.
Rectifying the filtrate, recovering solvent and methyltrimethoxysilane at normal pressure, and rectifying at-0.096 Mpa/115 deg.C to obtain methylphenyl dimethoxysilane with purity of 99.0%; the yield thereof was found to be 74.3%.
Comparative example 3
Adding 24 parts of magnesium powder and 45 parts of tetrahydrofuran solvent into a Grignard reaction kettle, dropwise adding 1.2 parts of bromobenzene, heating to 66 ℃, refluxing and starting the Grignard reaction, wherein the initiation time is 20min;
under the condition of maintaining reflux, uniformly adding a mixed solution consisting of 135 parts of chlorobenzene, 15 parts of bromobenzene and 75 parts of solvent tetrahydrofuran, dropwise adding for 1.5h, and cooling by introducing nitrogen gas to obtain a chlorobenzene grignard reagent;
adding 542 parts of methyltrimethoxysilane into a synthesis reaction kettle, heating to 66 ℃, dropwise adding a chlorobenzene grignard reagent into the synthesis reaction kettle, keeping the temperature after completing the dropwise adding of 1.5h, dropwise adding methyltrichlorosilane into the synthesis reaction kettle, and titrating to the pH =5; after the reaction was completed, the mixture was filtered.
MgCl 2 Yield 63.6 parts; 275 parts of methyltrimethoxysilane, 60.8% of recovery, 149.4 parts of methylphenyldimethoxysilane, 83% of yield.
Rectifying the filtrate, recovering solvent and methyltrimethoxysilane at normal pressure, and rectifying at-0.096 Mpa/115 deg.C to obtain methylphenyl dimethoxysilane with purity of 98.9%; the yield thereof was found to be 70.6%.
Comparative example 4
Adding 24 parts of magnesium powder and 45 parts of tetrahydrofuran solvent into a Grignard reaction kettle, dropwise adding 1.2 parts of bromobenzene, heating to 66 ℃, refluxing and starting the Grignard reaction, wherein the initiation time is 20min;
under the condition of maintaining reflux, uniformly adding a mixed solution consisting of 135 parts of chlorobenzene, 15 parts of bromobenzene and 75 parts of solvent tetrahydrofuran, dropwise adding for 1.5h, and cooling by introducing nitrogen gas to obtain a chlorobenzene grignard reagent;
542 parts of methyltrimethoxysilane is added into a synthesis reaction kettle, the temperature is raised to 66 ℃, the chlorobenzene grignard reagent is dripped into the synthesis reaction kettle, 1.5h is filtered after the dripping is finished, and a filter cake is washed twice by 200 parts of methyltrimethoxysilane.
MgCl 2 Yield 0 part; the yield of methyltrimethoxysilane was 311 parts, 51.2% and the yield of methylphenyldimethoxysilane was 140.8 parts and 78.2%.
Rectifying the filtrate, removing tetrahydrofuran at the normal pressure of 66 ℃, gradually heating to 100 ℃, increasing the viscosity of the filtrate, and continuously heating for solidification, wherein the yield of the methyl phenyl dimethoxy silane is 0%.
Comparative example 5
Adding 24 parts of magnesium powder and 36 parts of 2-methyltetrahydrofuran solvent into a Grignard reaction kettle, dropwise adding 0.24 part of bromobenzene, heating to 80 ℃, refluxing and starting the Grignard reaction, and initiating for 30min;
under the condition of maintaining reflux, uniformly adding mixed solution consisting of 145 parts of chlorobenzene, 3.2 parts of bromobenzene and 36 parts of solvent 2-methyltetrahydrofuran, dropwise adding for 2 hours, and cooling by introducing nitrogen gas to obtain a chlorobenzene grignard reagent;
272 parts of methyltrimethoxysilane is added into a synthesis reaction kettle, the temperature is raised to 80 ℃, a chlorobenzene grignard reagent is dripped into the synthesis reaction kettle, the temperature is kept after the dripping is finished for 2.5 hours, 150 parts of cyclohexane is added, diphenyldichlorosilane is dripped into the synthesis reaction kettle, and the pH is titrated to =5; after the reaction was completed, the mixture was filtered.
MgCl 2 Yield 53.1 parts; the recovery rate of methyltrimethoxysilane is 80 parts, and the recovery rate is 58.2%; the yield of methylphenyldimethoxysilane was 144.5 parts, and 80.3% of yield was obtained.
Rectifying the filtrate, recovering solvent and methyltrimethoxysilane at normal pressure, and rectifying at-0.096 Mpa/115 deg.C to obtain methylphenyl dimethoxysilane with purity of 98.5%; the yield thereof was found to be 60.2%.
Comparative example 6
Adding 24 parts of magnesium powder and 40 parts of tetrahydrofuran solvent into a Grignard reaction kettle, dropwise adding 0.48 part of bromobenzene, heating to 66 ℃, refluxing and starting the Grignard reaction, wherein the initiation time is 25min;
under the condition of maintaining reflux, uniformly adding mixed solution consisting of 135 parts of chlorobenzene, 6.5 parts of bromobenzene and 56 parts of solvent tetrahydrofuran, dropwise adding for 1.5h, and cooling by introducing nitrogen to obtain a chlorobenzene grignard reagent;
adding 362 parts of methyltrimethoxysilane into a synthesis reaction kettle, heating to 75 ℃, dropwise adding a chlorobenzene grignard reagent into the synthesis reaction kettle, preserving heat after dropwise adding is completed for 2 hours, adding 140 parts of n-heptane, dropwise adding trimethylchlorosilane into the synthesis reaction kettle, and titrating to pH =9.2; after the reaction was completed, the mixture was filtered.
MgCl 2 Yield 52 parts; the yield of methyltrimethoxysilane was 125.8 parts and 55.3%, and the yield of methylphenyldimethoxysilane was 144 parts and 80%.
Rectifying the filtrate, recovering solvent and methyltrimethoxysilane at normal pressure, and rectifying at-0.096 Mpa/115 deg.C to obtain methylphenyl dimethoxysilane with purity of 98.5%; the yield thereof was found to be 59.6%.

Claims (9)

1. A method for synthesizing methyl phenyl dimethoxy silane is characterized by comprising the following steps:
(1) Adding magnesium powder and a proper amount of ether solvent into a Grignard reaction kettle, dropwise adding bromobenzene, heating and refluxing to start the Grignard reaction;
(2) Under the condition of maintaining reflux, adding mixed solution consisting of chlorobenzene, bromobenzene and ether solvent into the Grignard reaction reagent obtained in the step (1) at a constant speed, and cooling by introducing nitrogen gas to obtain a Grignard reagent;
(3) Adding methyltrimethoxysilane into a synthesis reaction kettle, heating to 50-80 ℃, dropwise adding a chlorobenzene grignard reagent into the synthesis reaction kettle, preserving heat after dropwise adding is finished, adding a second solvent, adding chlorosilane into the synthesis reaction kettle, and preserving heat for reaction;
(4) Filtering after the reaction is finished, recovering the solvent and the methyltrimethoxysilane from the filtrate by normal pressure rectification, and then carrying out reduced pressure rectification to obtain the product of the methylphenyl dimethoxysilane.
2. The method for synthesizing methylphenyldimethoxysilane as claimed in claim 1, wherein the ether-based solvent used in step (1) and step (2) is tetrahydrofuran or 2-methyltetrahydrofuran.
3. The method for synthesizing methylphenyldimethoxysilane as claimed in claim 1, wherein the amount of bromobenzene for starting the grignard reaction in the step (1) is 1% -5% of the mass of magnesium powder, and the temperature of the heated reflux reaction is the boiling point of the ether solvent used, more specifically 60 ℃ -80 ℃.
4. The method for synthesizing methylphenyldimethoxysilane as claimed in claim 2, wherein the raw material charge amounts in the steps (1), (2) and (3) are 15 to 35 parts by mass of magnesium powder, 110 to 150 parts by mass of chlorobenzene, 3.0 to 20.0 parts by mass of bromobenzene, 70 to 120 parts by mass of ether solvent and 270 to 550 parts by mass of methyltrimethoxysilane.
5. The method for synthesizing methylphenyldimethoxysilane as defined in claim 4, wherein the mass ratio of bromobenzene in the step (1) to that in the step (2) is 0.01-0.1:0.2-1.0; the mass ratio of the ether solvent in the step (1) to the ether solvent in the step (2) is 1:1-5.
6. The method for synthesizing methylphenyldimethoxysilane as claimed in claim 1, wherein the second solvent used in the step (3) includes toluene, n-heptane, cyclohexane, n-hexane, and the amount of the second solvent is 100 to 150 parts.
7. The method for synthesizing methyldimethoxysilane according to claim 1, wherein in the step (3), the chlorosilane is methylchlorosilane or monophenylchlorosilane; the methylchlorosilane is methyl trichlorosilane, dimethyldichlorosilane or trimethylchlorosilane;
the monophenyl chlorosilane is phenyl trichlorosilane, methyl phenyl dichlorosilane or dimethyl phenyl chlorosilane.
8. The method for synthesizing methylphenyldimethoxysilane as claimed in claim 7, wherein the methylchlorosilane is methyltrichlorosilane; the monophenyl chlorosilane is methyl phenyl dichlorosilane.
9. The method for synthesizing methyldimethoxysilane according to claim 8, wherein the end point of the chlorosilane feed is that the pH of the raw material in the reaction vessel in the step (3) is 5 to 7.
CN202210951850.4A 2022-08-09 2022-08-09 Synthesis method of methyl phenyl dimethoxy silane Pending CN115448944A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210951850.4A CN115448944A (en) 2022-08-09 2022-08-09 Synthesis method of methyl phenyl dimethoxy silane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210951850.4A CN115448944A (en) 2022-08-09 2022-08-09 Synthesis method of methyl phenyl dimethoxy silane

Publications (1)

Publication Number Publication Date
CN115448944A true CN115448944A (en) 2022-12-09

Family

ID=84296227

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210951850.4A Pending CN115448944A (en) 2022-08-09 2022-08-09 Synthesis method of methyl phenyl dimethoxy silane

Country Status (1)

Country Link
CN (1) CN115448944A (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4777278A (en) * 1987-10-08 1988-10-11 Akzo America Inc. Synthesis of alkyl cycloalkyl dialkoxysilanes
CN101058585A (en) * 2007-05-22 2007-10-24 杭州师范大学 Safe separation method for increasing yield of methyl phenyl dialkoxy silicane
CN101717512A (en) * 2009-11-20 2010-06-02 苏州大学 Method for preparing methyl phenyl vinyl silicone resin
CN102161672A (en) * 2009-09-24 2011-08-24 仙桃市格瑞化学工业有限公司 Preparation method of triphenyl silanol
CN104017017A (en) * 2014-06-25 2014-09-03 四川科立鑫新材料有限公司 Method for synthesizing phenyl-containing organosilicon monomers
CN105732692A (en) * 2016-03-30 2016-07-06 湖北省化学工业研究设计院 Synthetic method of methyl phenyl dimethoxysilane

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4777278A (en) * 1987-10-08 1988-10-11 Akzo America Inc. Synthesis of alkyl cycloalkyl dialkoxysilanes
CN101058585A (en) * 2007-05-22 2007-10-24 杭州师范大学 Safe separation method for increasing yield of methyl phenyl dialkoxy silicane
CN102161672A (en) * 2009-09-24 2011-08-24 仙桃市格瑞化学工业有限公司 Preparation method of triphenyl silanol
CN101717512A (en) * 2009-11-20 2010-06-02 苏州大学 Method for preparing methyl phenyl vinyl silicone resin
CN104017017A (en) * 2014-06-25 2014-09-03 四川科立鑫新材料有限公司 Method for synthesizing phenyl-containing organosilicon monomers
CN105732692A (en) * 2016-03-30 2016-07-06 湖北省化学工业研究设计院 Synthetic method of methyl phenyl dimethoxysilane

Similar Documents

Publication Publication Date Title
KR900003953B1 (en) Process for producing alkoxysilanes
CN111793210B (en) Preparation method of RTV (room temperature vulcanized) silicone rubber tackifier
CN105801861B (en) The method of organosilicon high-boiling product preparation superfines silicone resin
CN106698441A (en) Treating method for residual liquid and slag slurry produced in polysilicon production
CN108715637B (en) Method for preparing polysiloxane by using tail gas of 3-chloropropyltrichlorosilane
CN115448944A (en) Synthesis method of methyl phenyl dimethoxy silane
CN109384233B (en) Method for treating silicon polymers
CN109320722B (en) Synthetic preparation method of MQ type organic silicon resin
EP2754664B1 (en) Method for preparing trialkoxysilane
CN111303198A (en) Method for preparing organosilane by using organic silicon byproduct
JP3656168B2 (en) Method for producing silicon compound bonded with halogen atom
CN111285896B (en) Preparation method of bis (N-methylbenzamide) ethoxymethylsilane
CN113943319B (en) Process for preparing dimethyl dichlorosilane by using organosilicon by-product
KR20170091623A (en) Method for recovering hexachlorodisilane from chlorosilane mixtures in process offgas streams
CN105732692B (en) The synthetic method of aminomethyl phenyl dimethoxysilane
CN113292592B (en) Method for removing impurities of methyldichlorosilane and silicon tetrachloride in trimethylchlorosilane
CN109251220A (en) A kind of preparation method of dimethyldimethoxysil,ne
CN110003266B (en) Environment-friendly production method of high-quality 3-octanoyl thio-1-propyltriethoxysilane
CN112480161B (en) Aminopropyl trimethoxy silane and preparation method thereof
CN107652317B (en) Method for preparing alpha, omega-dichloro end-capped siloxane by cracking reaction of silicon rubber series substances
CN116102018B (en) Method for separating hexachlorodisilane from polysilicon byproduct oligomeric chlorosilane
CN108440592B (en) Preparation method of 1, 5-divinyl-1, 1,3,3,5, 5-hexamethyl trisiloxane
CN113429573B (en) Method for preparing polydimethylsilane by ultrasonic sodium condensation and polydimethylsilane
CN114084889B (en) Method for preparing trisilylamine
CN111892560B (en) Recovery processing technology of tetrahydrofuran in step-by-step Grignard method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination