Process for producing low-color and color-stable isocyanatoorganosilanes and products derived therefrom

Patent metadata

Field	Value
Publication number	US-9663539-B2
Application number	US-201514797828-A
Country	US
Kind code	B2
Filing date	Jul 13, 2015
Priority date	Jul 14, 2014
Publication date	May 30, 2017
Grant date	May 30, 2017

Abstract

The invention herein is directed to a process for producing isocyanatoorganosilanes having low color and improved color stability over known isocyanatosilanes involving a neutralizing step in which a carbamatoorganosilane intermediate is neutralized with acid to a pH equal to or greater than 6.0, to the isocyanatosilane produced by said process and to coatings and numerous other industrial applications which are useful in numerous industries containing the isocyanatoorganosilane produced by the process.

First claim

The invention claimed is:

1. A process for producing isocyanatoorganosilane having low color and color stability comprising:
(a) reacting aminoorganosilane with organic carbonate ester in the presence of basic catalyst to form a reaction mixture containing silylorganocarbamate;
(b) neutralizing the reaction mixture of step (a) with an organic carboxylic acid to a pH value equal to or greater than 6.0;
(c) stripping the neutralized reaction mixture resulting from step (b) at a temperature of from about 80° C. to about 130° C. so as to provide less than about 5.0 weight percent organic carbonate ester based on the total weight of the stripped reaction mixture;
(d) filtering the stripped reaction mixture resulting from step (c);
(e) optionally adding an organic carboxylic acid to adjust the pH of the filtered reaction mixture resulting from step (d) to a value equal to or greater than about 6.0;
(f) thermally cracking the stripped reaction mixture containing silylorganocarbamate resulting from step (d) or step (e) to provide for an isocyanatoorganosilane and thermally cracked reaction byproducts;
(g) separating isocyanatoorganosilane from the thermally cracked reaction byproducts produced in step (f); and
(h) collecting the isocyanatoorganosilane from step (g) to provide for isocyanatoorganosilane having low color and color stability.

2. The process of claim 1 wherein the organic carbonate ester is less than about 0.1 percent by weight based on the total weight of the stripped reaction mixture.

3. The process of claim 1 wherein the aminoorganosilane is of the general Formula (1):
(R 2 O) 3-n R 3 n SiR 1 NH 2   (1)

wherein
R 1 is a divalent hydrocarbon group of from 1 to about 20 carbon atoms;
each R 2 and R 3 is independently selected from the group consisting of an alkyl group containing from 1 to about 20 carbon atoms, an alkoxyalkyl group containing from 3 to about 20 carbon atoms, alkyl groups substituted with at least one halo group containing from 1 to about 10 carbon atoms, a cycloalkyl group containing from 5 to about 10 carbon atoms, an aryl group containing from 6 to about 10 carbon atoms and an aralkyl group containing from 7 to about 10 carbon atoms; and
the subscript n is an integer of from 0 to 2.

4. The process of claim 1 wherein the organic carbonate ester is of the general
R 4 OC(═O)OR 4   (2)

wherein
each R 4 is independently a hydrocarbyl group containing up to about 20 carbon atoms, or a halohydrocarbyl group containing up to about 20 carbon atoms, or both R 4 groups together form a divalent alkylene group R 5 containing from about 2 to about 12 carbon atoms.

5. The process of claim 1 wherein the basic catalyst is an alkoxide of an alkali metal or alkaline earth metal.

6. The process of claim 1 wherein the silylorganocarbamate is of the general Formula (3):
(R 2 O) 3-n R 3 n SiR 1 NHC(═O)OR 6   (3)

wherein
R 1 is a divalent hydrocarbon group of from 1 to about 20 carbon atoms;
each R 2 and R 3 is independently selected from the group consisting of an alkyl group containing from 1 to about 20 carbon atoms, an alkoxyalkyl group containing from 3 to about 20 carbon atoms, an alkyl group substituted with at least one halo group containing from 1 to about 10 carbon atoms, a cycloalkyl group containing from 5 to about 10 carbon atoms, an aryl group containing from 6 to about 10 carbon atoms, and an aralkyl group containing from 7 to about 10 carbon atoms;
R 6 is R 4 or R 5 OH, wherein R 4 is a hydrocarbyl group containing up to about 20 carbon atoms, or a halohydrocarbyl group containing up to about 20 carbon atoms, and R 5 is an alkylene group containing from about 2 to about 12 carbon atoms;
and the subscript n is an integer of from 0 to 2.

7. The process of claim 1 wherein the molar ratio of organic carbonate ester to aminoorganosilane in step (a) is from about 1.0/1 to about 1.3/1.

8. The process of claim 1 where in step (b) the organic carboxylic acid is selected from the group consisting of glacial acetic acid, propionic acid, butyric acid, hexanoic acid, oleic acid, maleic acid, fumaric acid, succinic acid and mixtures thereof.

9. The process of claim 1 wherein the stripping step (c) is conducted at a temperature of from 80° C. to about 130° C.

10. The process of claim 1 wherein the stripping step (c) is conducted at a vacuum of up to about 90 mmHg.

11. The process of claim 10 wherein the stripping step (c) is conducted in a vacuum of from about 10 mmHg to about 50 mm Hg.

12. The process of claim 1 wherein the stripping step (c) is conducted for a time sufficient to remove alcohol byproduct and unreacted organocarbonate ester.

13. The process of claim 1 wherein the cracking step (f) is conducted at a temperature of from about 160° C. to about 230° C.

14. The process of claim 1 wherein the color stability of the isocyanatoorganosilane collected in step (h) is such that after being exposed to a heat of 100° C. for 24 hours, is equal to or less than 40 Pt—Co, as measured in accordance with ASTM D1209-05.

15. The process of claim 1 further comprising treating the isocyanatoorganosilane collected in step (h) with an ion exchange resin.

16. The process of claim 1 further comprising (i) utilizing the isocyanatosilane (h) in a coating composition.

17. The process of claim 16 wherein the coating composition of is an automotive or industrial coating.

18. The process of claim 17 wherein the automotive coating is an automotive clear coat.

19. The process of claim 1 wherein the neutralizing step (b) is conducted with an organic carboxylic acid to neutralize the silylorganocarbamate reaction product mixture to a pH of from 6.3 to 7.3.

Assignees

• Momentive Performance Mat Inc

Inventors

• Vu Dung-Thi
• Mendicino Frank Dominic
• Bahr Steven Roger
• Zhao Lina
• Kelby Jeffrey R
• Kumar Vikram
• Wilcox David Mark

Classifications

• C07F7/02 Primary

  Silicon compounds · CPC title

• C07F7/1892 Primary

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

• C09D175/04

  Polyurethanes · CPC title

• C08G18/603

  Polyamides · CPC title

• C08G18/0823

  containing carboxylate salt groups or groups forming them · CPC title