Method of preparing dialkyl-, diaryl-, and alkylaryl-dihalosilanes with high selectivity in a Grignard coupling reaction

Patent metadata

Field	Value
Publication number	US-9828394-B2
Application number	US-201414775816-A
Country	US
Kind code	B2
Filing date	Mar 14, 2014
Priority date	Mar 15, 2013
Publication date	Nov 28, 2017
Grant date	Nov 28, 2017

Abstract

A method of making a diakyl-, diaryl-, or alkylaryl-dihalosilane in a Grignard coupling reaction with a high degree of selectivity is provided. More specifically, a Grignard reagent comprising an alkyl- or aryl-magnesium halide is allowed to react with an alkyl- or aryl-trihalosilane precursor or reagent to produce a product mixture of R 2 SiX 2 and R 3 SiX, wherein each R is independently selected to be an alkyl or aryl group and X is a halogen group, such that the R 2 SiX 2 product is formed with a high degree of selectivity. High selectivity is defined as the mass ratio of R 2 SiX 2 product to the R 3 SiX product that is formed in the reaction being greater than 7:1.

First claim

The invention claimed is:

1. A method of making dialkyl-, diaryl-, or alkylaryl-dihalosilanes with a high degree of selectivity in a Grignard coupling reaction, the method comprising the steps of:
providing a reactor, the reactor selected as one from the group of a plug flow reactor (PFR), a continuous tube reactor (CTR), a piston flow reactor, and more than one continuous stirred tank reactor (CSTR) connected in series;
providing a hydrocarbon solvent stream at a predetermined flow rate to the reactor;
providing an alkyl- or aryl-trihalosilane stream at a predetermined flow rate to the reactor;
providing a Grignard reagent stream comprising an alkyl- or aryl-magnesium halide at a predetermined flow rate to the reactor;
allowing the solvent stream, alkyl- or aryl-trihalosilane stream, and Grignard reagent stream to combine to form a combined reactant stream;
wherein the flow rate of the solvent stream, alkyl- or aryl-trihalosilane stream, and the Grignard reagent stream are selected so that the mass ratio of the alkyl- or aryl-trihalosilane to the Grignard reagent in the combined reactant stream is greater than or equal to 1.5:1 and the mass ratio of the solvent to the Grignard reagent in the combined reactant stream is greater than or equal to 3:1;
allowing the combined reactant stream to react at a temperature from 10° C. to 80° C. to form a product mixture comprising R 2 SiX 2 , R 3 SiX, and a salt, wherein each R is independently selected to be an alkyl or aryl group, X is a halogen group, and the mass ratio of R 2 SiX 2 to R 3 SiX in the product mixture is greater than 7:1; and
optionally, collecting the product mixture.

2. The method according to claim 1 , wherein the reactor is a PFR comprising at least one fluidic module.

3. The method according to claim 1 , wherein the method further comprises the steps of:
measuring a baseline pressure drop across the reactor prior to starting the Grignard reaction;
monitoring the pressure drop across the reactor during the course of the Grignard reaction; and comparing the pressure drop across the reactor monitored during the course of the Grignard reaction to the baseline pressure drop in order to determine a change in the pressure drop;
wherein the change in pressure drop provides a measurement for the degree to which the reactor is plugged by salt that has agglomerated and settled in the reactor or that has deposited on the walls in the reactor.

4. The method according to claim 3 , wherein the method further comprises the steps of:
stopping the Grignard reaction;
removing the salt plugging the reactor; and
restarting the Grignard reaction.

5. The method according to claim 4 , wherein removing the salt plugging the reactor further comprises the steps of:
isolating the plugged portion of the reactor from the rest of the reactor;
flushing hydrocarbon solvent through the isolated portion of the reactor to remove the alkyl- or aryl-trihalosilane;
flushing water through the isolated portion of the reactor until all the salts are removed;
flushing an alcohol through the isolated portion of the reactor to remove any residual water;
flushing the hydrocarbon solvent through the isolated portion of the reactor again to purge the alcohol from the isolated portion; and
reestablishing contact between the isolated portion of the reactor and the rest of the reactor.

6. The method according to claim 1 , wherein the combined reactant stream has a flow rate that is predetermined based on the size of the reactor such that the average amount of time that the combined reactant stream resides in the reactor is less than 30 seconds.

7. The method according to claim 6 , wherein the residence time for the combined reactant stream in the reactor is less than 20 seconds.

8. The method according to claim 1 , wherein the mass ratio of solvent to Grignard reagent is greater than 5:1.

9. The method according to claim 1 , wherein the mass ratio of R 2 SiX 2 to R 3 SiX in the product mixture is greater than 12:1.

10. The method according to claim 1 , wherein the Grignard reagent stream is a solution comprising the Grignard reagent dispersed in a solvent;
wherein the amount of Grignard reagent present in the solution is less than 75 wt. % based on the overall weight of the solution.

11. The method according to claim 1 , wherein the solvent is toluene, the Grignard reagent is phenylmagnesium chloride (PhMgCl), the alkyl- or aryl-trihalosilane is methyltrichlorosilane (MeSiCl 3 ), and the product mixture formed comprises PhMeSiCl 2 , Ph 2 MeSiCl, and MgCl 2 .

Assignees

• Dow Corning

Inventors

• Lee James
• Nguyen Binh Thanh
• Pider Scott E
• Umphrey Steven L
• Vo Hanh Xuan

Classifications

• C07F7/12 Primary

  Organo silicon halides · CPC title

• C07F7/122

  by reactions involving the formation of Si-C linkages (hydrosilylation reactions C07F7/14; direct synthesis C07F7/16) · CPC title

• C07F7/125 Primary

  by reactions involving both Si-C and Si-halogen linkages, the Si-C and Si-halogen linkages can be to the same or to different Si atoms, e.g. redistribution reactions · CPC title