Process for the direct synthesis of trialkoxysilane
View Patent ↗This invention discloses a process to improve reaction stability in the Direct Synthesis of trialkoxysilanes. The process is particularly effective in the Direct Synthesis of triethoxysilane and its higher alkyl cognates providing improved triethoxysilane yields.
1. A process for the Direct Synthesis of trialkoxysilane comprising the steps of:
a) forming a reaction mixture comprising a thermally stable solvent, silicon metal and a catalytically effective amount of a nanosized copper catalyst precursor;
b) agitating and heating the reaction mixture to form copper-activated silicon therein; and,
c) adding to the reaction mixture
(i) an alcohol R 1 OH wherein R 1 is an alkyl group containing from 1 to 6 carbon atoms,
(ii) a catalyst-promoting amount of at least one CN-containing promoter, wherein the promoter possesses the general formula X-(CN) n wherein X is a hydrocarbon group R 2 of valence n containing from 1 to 40 carbon atoms, and optionally, silicon and/or etheric oxygen, and n is an integer with the value of 1 to 4,
the alcohol reacting with the copper-activated silicon to provide trialkoxysilane HSi(OR 1− ) 3 wherein R 1 is as defined.
2. The process of claim 1 wherein the nanosized copper catalyst precursor is selected from the group consisting of nanosized copper, nanosized copper oxides, nanosized copper chlorides, other nanosized copper salts, and mixtures thereof.
3. The process of claim 2 wherein the nanosized copper catalyst precursor has diameters in the range from 1 nanometer (10 −9 meter) to 100 nanometer (10 −7 meter).
4. The process of claim 1 wherein the nanosized copper catalyst precursor is selected from the group comprising copper, copper (I) oxide, copper (II) oxide, copper (I) chloride, copper (II) chloride, copper (II) hydroxide, basic cupric oxide, basic copper carbonate, copper carboxylate, copper alkoxide and mixtures thereof.
5. The process of claim 1 wherein the mixture of step (b) is heated from 150° C. to 350° C.
6. The process of claim 1 wherein n is 1 and R 2 is monovalent hydrocarbon group of up to 10 carbon atoms.
7. The process of claim 6 wherein the promoter is at least one member selected from the group consisting of acetonitrile, t-butyl nitrile, cyclohexyl nitrile, benzonitrile, benzyl nitrile, and mixtures thereof.
8. The process of claim 1 wherein n is 1 and R 2 an etheric oxygen-containing group R 3 OR 4 in which R 3 is a monovalent hydrocarbon group and R 4 is a divalent hydrocarbon group, there being up to about 40 carbon atoms total in the etheric oxygen-containing group.
9. The process of claim 1 wherein n is 2 and R 2 is an etheric oxygen-containing group R 5 OR 6 in which R 5 and R 6 divalent hydrocarbon groups, there being up to about 40 carbon atoms total in the etheric oxygen-containing group.
10. The process of claim 1 wherein n is 1 and R 2 is
in which each R 7 is the same or different monovalent hydrocarbon group of up to about 12 carbon atoms, one or more of which optionally contain etheric oxygen, R 8 is a divalent hydrocarbon group of up to about 10 carbon atoms and m is 0 or 1.
11. The process of claim 10 wherein at least one R 7 is selected from the group consisting of methoxy, ethoxy and propoxy.
12. The process of claim 1 wherein n is 2 and R 2 is
in which each R 9 is the same or different monovalent hydrocarbon group of up to about 12 carbon atoms, one or both of which optionally contain etheric oxygen, each R 10 is the same or different divalent hydrocarbon group of up to about 10 carbon atoms and p is 0 or 1.
13. The process of claim 12 wherein at least one R 9 is selected from the group consisting of methyl, ethyl and propyl.
14. The process of claim 1 wherein n is 3 and R 2 is
in which each R 11 is the same or different monovalent hydrocarbon group of up to about 12 carbon atoms, one or both of which optionally contain etheric oxygen, each R 12 is the same or different divalent hydrocarbon group of up to about 10 carbon atoms and p is 1.
15. The process of claim 14 wherein at least one R 11 is selected from the group consisting of methyl, ethyl and propyl.
16. The process of claim 1 wherein at least one promoter wherein X is hydrogen or a metal is combined with at least on promoter where X is R 2 .
17. The process of claim 1 wherein the promoter is a catalyst-promoting amount of acetonitrile and CuCl.
18. The process of claim 9 wherein the promoter is selected from the group consisting of CH 2 (CN) 2 , 1,1-dicyanocyclohexane, 1,2-dicyanobenzene and 1,4-dicyanocyclohexane, and mixtures thereof.
19. The process of claim 14 wherein the promoter is selected from the group consisting of 2,4,6-tricyanotoluene, 1,3,5-tricyanobenzene, tricyanoethoxypropane, and mixtures thereof.
20. The process of claim 1 wherein the promoter is selected from the group consisting of 1,1,2,2-tetracyanoethane, 1,2,4,5-tetracyanobenzene, and 2,2,3,3-tetracyanoethylene oxide, and mixtures thereof.
21. The process of claim 1 wherein the promoter has a particle size from about 10 micrometers to about 0.1 nanometer.
22. The process of claim 21 wherein the promoter has a particle size that is less than about 1 micrometer.
23. The process of claim 16 wherein the promoter is a mixture of CuCN and CH 3 (CH 2 ) 10 CN.
24. The process of claim 16 wherein the promoter is a mixture of CuCN and CN(CH 2 ) 6 CN.
25. The process of claim 1 wherein the promoter is present in an amount of about 100 parts per million to about 10 weight percent of the weight of silicon.
26. The process of claim 25 wherein the promoter is present in an amount from about 1000 parts per million to about 4 weight percent of the silicon.
27. The process of claim 5 wherein the promoter is present in an amount from about 100 parts per million to 6 weight percent of the silicon.
28. The process of claim 27 wherein the promoter is present in an amount from about 200 parts per million to about 4 weight percent of the silicon.
29. The process of claim 1 further comprising a foam control agent.
30. The process of claim 1 wherein the reaction temperature of step (c) is maintained at from 200° C. to 280° C.
31. The process of claim 1 wherein the silicon metal having a particle size of less than about 500 micron; one or more copper catalyst precursors having an average particle size from about 0.1 nm to about 600 nm, a surface area as low as 0.1 m 2 /g, in an amount from about 0.01 to about 5 parts by weight per 100 parts of said silicon metal such that about 0.008 to about 4.5 parts elemental copper is present based on 100 parts by weight of said silicon metal; the catalyst-promoting amount at least one promoter is from about 0.02 to about 6 parts by weight per 100 parts of said silicon metal; and a thermally stable reaction solvent present in an amount that provides a gravimetric ratio of solids to solvent of about 1:2 to about 1:4.
32. A trialkoxysilane produced by the process of claim 1 .
33. A trialkoxysilane produced by the process of claim 1 .
34. A trialkoxysilane produced by the process of claim 31 .
35. A process for the Direct Synthesis of trialkoxysilane comprising the steps of:
a) forming a reaction mixture comprising a thermally stable solvent, silicon metal and a catalytically effective amount of a copper catalyst precursor;
b) agitating and heating the reaction mixture to form copper-activated silicon therein; and,
c) adding the reaction mixture
(i) an alcohol R 1 OH wherein R 1 is an alkyl group containing from 1 to 6 carbon atoms,
(ii) a catalyst-promoting amount of at least one CN-containing promoter, wherein the promoter possesses the general formula X—(CN) n wherein X is a hydrocarbon group R 2 of valence n containing from 1 to 40 carbon atoms, and optionally, silicon and/or etheric oxygen, and n is an integer with the value of 1 to 4;
the alcohol reacting with the copper-activated silicon to provide trialkoxysilane HSi(OR 1 ) 3 wherein R 1 is defined.
36. A process for the Direct Synthesis of trialkoxysilane comprising the steps of:
a) forming a reaction mixture comprising
i) a thermally stable solvent in an amount that provides a gravimetric ratio of solids to solvent of about 1:2 to about 1:4,
ii) silicon metal having a particle size of less than about 500 microns; and
iii) a catalytically effective amount of a nanosized copper catalyst precursor having an average particle size from 0.1 nm to 600 nm and BET surface area of at least 0.1 m 2 /gram and in the amount from 0.01 to 5 parts by weight per 100 parts by weight a said silicon metal such that 0.008 to 4.5 parts elemental copper per 100 parts of said silicon metal;
b) agitating and heating the reaction mixture to a temperature of between 190° C. to 350° to form nanosized copper catalysts precursor with an average particle size in the rang of from 1 nm to 100 nm which reacts with silicon metal to form a copper-activated silicon therein; and,
c) adding to the reaction mixture maintained at a temperature from 190° C. to 240° C.
i) an alcohol R 1 OH wherein R 1 is an alkyl group containing from 2 to 6 carbon atoms,
ii) a catalyst-promoting amount of at least one CN-containing promoter, wherein the promoter possesses the general formula X—(CN) n wherein X is a hydrogen or a metal with a valence of n and n is an integer with the value of 1 to 4;
the alcohol reacting with the copper-activated silicon to provide trialkoxysilane HSi(OR 1 ) 3 wherein R 1 is defined.
37. The process of claim 35 wherein the CN-containing promoter is selected from the group consisting of HCN, LiCN, NaCN, KCN, Ca(CN) 2 , Mg(CN) 2 , and Si(CN) 4 .
38. The process of claim 35 wherein the CN-containing promoter is selected from the group consisting of Cu(CN), Pd(CN) 2 , Ag(CN) and Ni(CN) 2 .