Process for preparing an acryloyloxysilane

Patent metadata

Field	Value
Publication number	US-10273254-B2
Application number	US-201615567272-A
Country	US
Kind code	B2
Filing date	Jun 17, 2016
Priority date	Jun 19, 2015
Publication date	Apr 30, 2019
Grant date	Apr 30, 2019

Abstract

A process for preparing an acryloyloxysilane, comprising: reacting a metal salt of a carboxylic acid having the formula

[CR 2 2 ═CR 1 CO − ] a M a+   (I),

with a haloorganoalkoxysilane having the formula

XR 3 Si(OR 4 ) n R 5 3-n   (II)

at a temperature of from 50 to 160° C. and in the presence of a catalyst, and in the presence of water, an alcohol comprising 1 to 5 carbon atoms, or a combination of water and an alcohol comprising 1 to 5 carbon atoms, to form a mixture comprising an acryloyloxysilane and a metal halide having the formula

M a+ X − a   (III),

wherein R 1 is H, R 7 COO − M a+ , or C 1 -C 6 hydrocarbyl, each R 2 is independently R 1 or [COO − ]M a+ , M a+ is an alkali metal cation or alkaline earth metal cation, a is 1 or 2, X is halo, R 3 is C 1 -C 6 hydrocarbylene, each R 4 is independently C 1 -C 10 hydrocarbyl, each R 5 is independently R 1 and n is an integer from 1 to 3.

First claim

That which is claimed is:

1. A process for preparing an acryloyloxysilane, the process comprising:
1) heating, at a temperature of from 50 to 115° C.
a metal salt of a carboxylic acid having the formula
[CR 2 2 ═CR 1 COO − ] a M a+   (I),

a haloorganoalkoxysilane having the formula
XR 3 Si(OR 4 ) n R 5 3-n   (II),

a catalyst, and
a combination of 2100 to 3500 ppmw water and 3100 to 3500 ppmw methanol, to form a mixture comprising an acryloyloxysilane and a metal halide having the formula
M a+ X − a   (III),

 wherein R 1 is H, R 7 COO − M a+ , or C 1 -C 6 hydrocarbyl, each R 2 is independently R 1 or [COO − ]M a+ , M a+ is an alkali metal cation or alkaline earth metal cation, a is 1 or 2, X is halo, R 3 is C 1 - C 6 hydrocarbylene, each R 4 is independently C 1 -C 10 hydrocarbyl, each R 5 is independently R 1 , R 7 is hydrocarbylene having from 1 to 6 carbon atoms, and n is an integer from 1 to 3; and

2) removing at least a portion of the metal halide from the mixture by filtration.

2. The process of claim 1 , wherein the acryloyloxysilane has the formula
CR 6 2 ═CR 1 COOR 3 Si(OR 4 ) n R 5 3-n   (IV),

wherein R 1 , R 3 , R 4 , R 5 , and n are as defined in claim 1 , and wherein each R 6 is independently H, C 1 -C 6 hydrocarbyl, or
COOR 3 Si(OR 4 ) n R 5 3-n , wherein R 3 , R 4 , R 5 , and n are as defined in claim 1 .

3. The process of claim 1 , wherein M a+ is a sodium ion or potassium ion, a is 1, and X is chloro.

4. The process of claim 1 , wherein each R 1 is independently H, methyl, or [CH 2 COO − ]M a+ , each R 2 is independently H, methyl, or [COO − ]M a+ , R 3 is methylene, ethylene, or propylene, each R 4 is independently methyl or ethyl, each R 5 is independently H, methyl, or ethyl, R 7 is methylene, ethylene, or propylene, and n is 3.

5. The process of claim 1 , wherein the catalyst is tetrabutylammonium bromide.

6. The process of claim 1 , wherein the metal salt of a carboxylic acid is selected from the metal salt fumaric acid, sorbic acid, or acrylic acid.

7. The process of claim 1 wherein the acryloyloxysilane is γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-sorbyloxypropylmethyldimethoxysilane, γ-sorbyloxypropyltrimethoxysilane, γ-acryloyloxypropyltriethoxysilane, γ-sorbyloxypropyltriethoxysilane, bis(γ-trimethoxysilylpropyl) fumarate, or bis(γ-triethoxysilylpropyl) fumarate.

8. The process of claim 1 , wherein the heating is done in the presence of a non-polar solvent, wherein the non-polar solvent comprises a hydrocarbon having from 5 to 20 carbon atoms.

9. The process of claim 8 , wherein the non-polar solvent comprises less than 5% aromatic compounds.

10. The process of claim 1 , wherein heating is conducted in a reactor, wherein the metal salt of the unsaturated carboxylic acid, catalyst, a portion of the haloorganoalkoxysilane, and, if present, alcohol, water, co-catalyst, inhibitors and non-polar solvent, are added to the reactor and heated, and wherein after the heating, the remaining amount of haloorganoalkoxysilane is added to the reactor.

11. A process for preparing an acryloyloxysilane, the process comprising:
1) heating, at a temperature of from 50 to 160° C.
a metal salt of a carboxylic acid having the formula
[CR 2 2 ═CR 1 COO − ] a M a+   (I),

a haloorganoalkoxysilane having the formula
XR 3 Si(OR 4 ) n R 5 3-n   (II),

a catalyst, and one of
i) a combination of 400 ppmw to 3,500 ppmw water and 4500 to 5600 ppmw methanol, or
ii) a combination of 1100 to 3500 ppmw water and 3100 to 3500 ppwm methanol,

to form a mixture comprising an acryloyloxysilane and a metal halide having the formula
M a+ X − a   (III),

wherein R 1 is H, R 7 COO − M a+ , or C 1 -C 6 hydrocarbyl, each R 2 is independently R 1 or [COO − ]M a+ , M a+ is an alkali metal cation or alkaline earth metal cation, a is 1 or 2, X is halo, R 3 is C 1 -C 6 hydrocarbylene, each R 4 is independently C 1 -C 10 hydrocarbyl, each R 5 is independently R 1 , R 7 is hydrocarbylene having from 1 to 6 carbon atoms, and n is an integer from 1 to 3; and
2) removing at least a portion of the metal halide from the mixture by filtration.

12. The process of claim 11 , wherein M a+ is a sodium ion or potassium ion, a is 1, and X is chloro.

13. The process of claim 11 , wherein each R 1 is independently H, methyl, or [CH 2 COO − ]M a+ , each R 2 is independently H, methyl, or [COO − ]M a+ , R 3 is methylene, ethylene, or propylene, each R 4 is independently methyl or ethyl, each R 5 is independently H, methyl, or ethyl, R 7 is methylene, ethylene, or propylene, and n is 3.

14. The process of claim 11 , wherein the catalyst is tetrabutylammonium bromide.

15. The process of claim 11 , wherein the metal salt of a carboxylic acid is selected from a metal salt of fumaric acid, sorbic acid, or acrylic acid.

16. The process of claim 11 , wherein the acryloyloxysilane is γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-sorbyloxypropylmethyldimethoxysilane, γ-sorbyloxypropyltrimethoxysilane, γ-acryloyloxypropyltriethoxysilane, γ-sorbyloxypropyltriethoxysilane, bis(γ-trimethoxysilylpropyl) fumarate, or bis(γ-triethoxysilylpropyl) fumarate.

17. The process of claim 11 , wherein the heating is done in the presence of a non-polar solvent, wherein the non-polar solvent comprises a hydrocarbon having from 5 to 20 carbon atoms.

Assignees

• Dow Corning

Inventors

• Depierro Michael A
• Halpern Marc
• Jackson Thomas J
• Kloet Karen J
• Sprague Aaron R

Classifications

• C07F7/1804

  Compounds having Si-O-C linkages (Si-O-acyl linkages C07F7/1896) · CPC title

• C07F7/20 Primary

  Purification, separation · CPC title

• C07F7/1896

  Compounds having one or more Si-O-acyl linkages · CPC title

• C07F7/1892 Primary

  by reactions not provided for in C07F7/1876 - C07F7/1888 · CPC title