Granted Patent B2

US 7,825,243 · App. 11/144,464 · Granted Nov 2, 2010

Abstract

Claims (33)

1. A continuous process for the concurrent production of isocyanantosilane in a cracking reaction zone and silylisocyanurate in a trimerization zone, which comprises:

a) continuously providing a silylorganocarbamate of the general formula;

R a 1 SiX (3-a) RNHCOOR 2 ,

wherein R is a divalent hydrocarbon group of from 2 to 11 carbon atoms; R 1 is an alkyl or halogenated alkyl group of from 1 to 8 carbon atoms, an aryl group of at least 6 carbon atoms or an aralkyl group of at least 7 carbon atoms; R 2 is an alkyl group having 1 to 8 carbon atoms; X is a hydrolysable alkoxy group; and a is an integer from 0 to 3 to a cracking reaction medium comprising silylorganocarbamate, in the absence or, optionally, in the presence of a catalytically effective amount of cracking catalyst selected from the group consisting of ammonium carboxylate, alkali metal carboxylate and alkaline earth metal carboxylate, in a cracking reaction zone;

b) subjecting the cracking reaction medium in the cracking reaction zone to cracking reaction conditions to provide isocyanatosilane of general formula:

R a 1 SiX (3-a) RNCO,

wherein R is a divalent hydrocarbon group of 2 to 11 carbon atoms, R 1 is an alkyl or halogenated alkyl group of from 1 to 8 carbon atoms, an aryl group of at least 6 carbon atoms or an aralkyl group of at least 7 carbon atoms; X is a hydrolysable alkoxy group; and a is an integer from 0 to 3, and by-product alkanol of general formula:

R 2 OH

wherein R 2 is an alkyl group having 1 to 8 carbon atoms;

c) recovering isocyanatosilane and by-product alkanol from the cracking reaction zone;

d) purging continuously a portion of the cracking reaction medium during the cracking reaction;

e) introducing purged cracking reaction medium to a trimerization reaction zone; and,

f) subjecting the purged cracking reaction medium in the trimerization reaction zone to trimerization reaction conditions to provide silyisocyanurate of general formula;

wherein R is a divalent hydrocarbon group of from 2 to 11 carbon atoms; R 1 is an alkyl or halogenated alkyl group of from 1 to 8 carbon atoms, an aryl group of at least 6 carbon atoms or an aralkyl group of at least 7 carbon atoms; X is a hydrolysable alkoxy group; and a is an integer from 0 to 3 and by-product alkanol of general formula:

R 2 OH

wherein R 2 is an alkyl group having 1 to 8 carbon atoms.

2. The process of claim 1 wherein the cracking reaction zone is operated under liquid phase conditions.

3. The process of claim 1 wherein the silylorganocarbamate is at least one of methyl N-3-(trimethoxysilyl)-propylcarbamate, ethyl N-3-(trimethoxysilyl)propylcarbamate, methyl N-3-(triethoxysilyl)propylcarbamate, methyl N-3-(methyldimethoxysilyl)-propylcarbamate, methyl N-3-(dimethylmethoxysilyl)-propylcarbamate, methyl N-3-(triethoxysilyl)propylcarbamate, ethyl N-3-(triethoxysilyl)-propylcarbamate, methyl N-3-(methoxydiethoxysilyl)propylcarbamate, methyl N-3-(trimethoxysilyl) butylcarbamate and methyl N-3-(triethoxysilyl)-butylcarbamate, the isocyanatosilane is at least one of 3-isocyanato propyltrimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, isocyanatobutyltrimethoxysilane, isocyanatobutylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane, isocyanatopropylethyldiethoxysilane, isocyanatopropyldimethylmethoxysilane, isocyanatopropylmethoxydiethoxysilane, isocyanatobutyltriethoxysilane and isocyanatopropylphenylmethylmethoxysilane and the silyisocyanurate is at least one of 1,3,5-tris(trimethoxysilylpropyl)isocyanurate, 1,3,5-tris(methyldimethoxysilylpropyl)isocyanurate, 1,3,5-tris(trimethoxysilylbutyl)isocyanurate, 1,3,5-tris(methyldimethoxysilylbutyl)isocyanurate, 1,3,5-tris(triethoxysilyl-propyl)isocyanurate and 1,3,5-tris(phenylmethylmethoxysilylpropyl)isocyanurate.

4. The process of claim 1 wherein the carboxylate salt is an alkali metal carboxylate salt of a carboxylic acid of from 1 to about 20 carbon atoms.

5. The process of claim 1 wherein the carboxylate salt is an alkali metal carboxylate salt of a carboxylic acid of from 1 to about 12 carbon atoms.

6. The process of claim 1 wherein the carboxylate salt is selected from the group consisting of lithium formate, sodium formate, potassium formate, lithium acetate, sodium acetate, potassium acetate, lithium propanoate, sodium propanoate, potassium propanoate, and mixtures thereof.

7. The process of claim 1 wherein the silylorganocarbamate contains alkali metal carboxylate salt and is obtained by the process which comprises reacting an aminosilane with a dialkylcarbonate in the presence of alkali metal alkoxide catalyst to provide silylorganocarbamate and neutralizing the alkali metal alkoxide with carboxylic acid to produce alkali metal carboxylate salt which remains in the silylorganocarbamate to function as cracking catalyst in the cracking reaction zone.

8. The process of claim 7 wherein the alkali metal alkoxide is at least one of sodium methoxide, sodium ethoxide, sodium propoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium propoxide or potassium tert-butoxide and the carboxylic acid is at least one of formic acid, acetic acid and propanoic acid.

9. The process of claim 7 wherein the silylorganocarbamate contains from about 0.01 to about 0.5 weight percent alkali metal carboxylate.

10. The process of claim 7 wherein the silylorganocarbamate contains from about 0.05 to about 0.2 weight percent alkali metal carboxylate.

11. The process of claim 7 wherein the alkali metal carboxylate salt is selected from the group consisting of lithium formate, sodium formate, potassium formate, lithium acetate, sodium acetate, potassium acetate, lithium propanoate, sodium propanoate, potassium propanoate, and mixtures thereof.

12. The process of claim 1 wherein the reaction conditions in the cracking reaction zone include a residence time therein of from about 1 minute to about 24 hours, a temperature of from about 140° C. to about 500° C. and a pressure of from about 5 to about 500 millimeters Hg.

13. The process of claim 1 wherein the reaction conditions in the cracking reaction zone include a residence time therein of from about 15 minutes to about 1 hour, a temperature of from about 180° C. to about 220° C. and a pressure of from about 50 to about 300 millimeters Hg.

14. The process of claim 1 wherein the reaction conditions in the trimerization zone are the same as, or different from, those employed in the cracking operation and include a residence time therein of from about 30 minutes to about 24 hours, a temperature of from about 150° C. to about 300° C. and a pressure of from about 50 to 300 millimeters Hg.

15. The process of claim 1 wherein during cracking, from about 1 to about 70 weight percent of the cracking reaction medium is purged based on the weight of the incoming silylorganocarbamate feed continuously purged from the cracking zone.

16. The process of claim 1 wherein during cracking from about 10 to about 50 weight percent of cracking reaction medium is based on the weight of the incoming silylorganocarbamate feed continuously purged from the cracking zone.

17. The process of claim 1 wherein no cracking catalyst is present in the cracking zone.

18. The process of claim 1 wherein recovering isocyanatosilane and by-product alkanol from the cracking reaction zone of step (c) through the use of a rectification column.

Assignments (22)