Process for the production of organohydridochlorosilanes

Patent metadata

Field	Value
Publication number	US-11008349-B2
Application number	US-201816647773-A
Country	US
Kind code	B2
Filing date	Sep 20, 2018
Priority date	Sep 20, 2017
Publication date	May 18, 2021
Grant date	May 18, 2021

Abstract

The invention relates to a process for the manufacture of organomonosilanes, in particular, bearing both hydrogen and chlorine substituents at the silicon atom by subjecting a silane substrate comprising one or more organomonosilanes, with the proviso that at least one of these silanes has at least one chlorine substituent at the silicon atom, to the reaction with one or more metal hydrides selected from the group of an alkali metal hydride and an alkaline earth metal hydride in the presence of one or more compounds (C) acting as a redistribution catalyst.

First claim

The invention claimed is:

1. A process for the manufacture of monosilanes of the general formula (I):
R x SiH y Cl z   (I),

wherein R is an organyl group,
x=1 to 3,
y=1 to 3,
z=0 to 3, and
x+y+z=4,

comprising:
A) the step of subjecting a silane substrate comprising one or more monosilanes of the general formula (II)
R a SiH b Cl c   (II)

wherein R is as defined above,
a=1 to 3,
b=0 to 3,
c=0 to 3, and
a+b+c=4,
with the proviso that at least one silane of the general formula (II) has at least one chlorine substituent at the silicon atom,
to the reaction with one or more metal hydrides selected from the group consisting of an alkali metal hydride and an alkaline earth metal hydride,
in the presence of one or more compounds (C) selected from the group consisting of:
R 1 4 PCl, wherein R 1 is selected from the group consisting of hydrogen and an organyl group, which can be the same or different,
phosphines R 1 3 P, wherein R 1 is selected from the group consisting of hydrogen and an organyl group and can be the same or different,
amines R 1 3 N, wherein R 1 is selected from the group consisting of hydrogen and an organyl group and can be the same or different,
N-heterocyclic amines, and
ammonium compounds, and
B) optionally a step of separating the resulting monosilanes of the general formula (I) from the reaction mixture, and
wherein the monosilanes of the general formula (II) subjected to the reaction in step A) are formed by in situ cleavage of one or more compounds selected from the group consisting of

a) disilanes of the general empirical formula (III)
R e Si 2 H f Cl g   (III)

wherein R is an organyl group,
e=1 to 5,
f=0 to 5,
g=0 to 5 and
e+f+g=6, and

b) carbodisilanes of the general empirical formula (IV)
R m (SiCH 2 Si)H n Cl o   (IV)

wherein R is as defined above,
m=1 to 5,
n=0 to 5,
o=0 to 5 and
m+n+o=6.

2. The process according to claim 1 , wherein step A) is carried out in one or more organic solvents.

3. The process of claim 1 wherein all silanes of the formula (II) in step A) have at least one chlorine substituent at the silicon atom.

4. The process of claim 1 wherein in general formula (I) and one or more of the silanes of the general formula (II), R is an alkyl or cycloalkyl group.

5. The process of claim 1 wherein the silane substrate comprises more than about 90 wt-% of one single (or specific) silane of the formula (II) having at least one chlorine substituent at the silicon atom based on the total weight of the silane substrate.

6. The process of claim 1 wherein the silane substrate comprises more than about 90 wt-% of one single (or specific) silane of the formula (II) having no hydrogen substituent at the silicon atom based on the total amount of the silane substrate.

7. The process of claim 1 wherein the step A) is conducted at a temperature of about 0° C. to about 300° C.

8. The process of claim 1 wherein the methyl monosilanes of the formula (I) are selected from the group consisting of Me 2 SiHCl, MeSiHCl 2 and MeSiH 2 Cl.

9. The process of claim 1 , wherein the silanes of the general formula (II) are selected from the group consisting of Me 2 SiCl 2 and MeSiCl 3 .

10. The process of claim 1 wherein step A) is carried out in the presence of at least one compound (C) of the formula R 1 4 PCl wherein R 1 is as defined above.

11. The process of claim 1 wherein step A) is carried out in the presence of at least one compound of the formula R 1 4 PCl and the metal hydride is lithium hydride.

12. The process of claim 1 wherein in step A) Me 2 SiHCl is produced by the reaction of Me 2 SiCl 2 with lithium hydride in the presence of at least one compound of the formula R 1 4 PCl, in an ether compound having a boiling point at 1.01325 bar of at least 70° C.

13. The process of claim 1 wherein in step A) MeSiHCl 2 is produced by the reaction of MeSiCl 3 with lithium hydride in the presence of at least one compound of the formula R 1 4 PCl, in an ether compound having a boiling point at 1.01325 bar of at least 70° C.

14. The process of claim 1 wherein the step of separating the resulting monosilanes of the formula (I) is carried out by distillation and/or condensation.

15. The process of claim 2 , wherein the organic solvents are selected from the group consisting of 1,4-dioxane, diglyme, tetraglyme and mixtures thereof.

16. The process of claim 1 wherein the in situ cleavage is carried out in the presence of at least one compound (c) of the formula R 1 4 PCl.

17. The process of claim 11 wherein step A) is carried out in the presence of n-Bu 4 PCl.

18. The process of claim 12 wherein in step A) Me 2 SiHCl is produced by the reaction of Me 2 SiCl 2 with lithium hydride in the presence of n-Bu 4 PCl in diglyme as solvent.

19. The process of claim 13 wherein in step A) MeSiHCl 2 is produced by the reaction of MeSiCl 3 with lithium hydride in the presence of n-Bu 4 PCl in diglyme as solvent.

20. A process for the manufacture of monosilanes of the general formula (I):
R x SiH y Cl z   (I),

wherein R is an organyl group,
x=1 to 3,
y=1 to 3,
z=0 to 3, and
x+y+z=4,

comprising:
A) the step of subjecting a silane substrate comprising one or more monosilanes of the general formula (II)
R a SiH b Cl c   (II)

wherein R is as defined above,
a=1 to 3,
b=0 to 3,
c=0 to 3, and
a+b+c=4,
with the proviso that at least one silane of the general formula (II) has at least one chlorine substituent at the silicon atom,
to the reaction with one or more metal hydrides selected from the group consisting of an alkali metal hydride and an alkaline earth metal hydride,
in the presence of one or more compounds (C) selected from the group consisting of:
R 1 4 PCl, wherein R 1 is selected from the group consisting of hydrogen and an organyl group, which can be the same or different, and
phosphines R 1 3 P, wherein R 1 is selected from the group consisting of hydrogen, unsubstituted alkyl, cycloalkyl, alkenyl and aryl, which can be the same or different, and
(B) optionally a step of separating the resulting monosilanes of the general formula (I) from the reaction mixture.

21. A process for the manufacture of monosilanes of the general formula (I):
R x SiH y Cl z   (I),

wherein R is an organyl group,
x=1 to 3,
y=1 to 3,
z=0 to 3, and
x+y+z=4,

comprising:
A) the step of subjecting a silane substrate comprising one or more monosilanes of the general formula (II)
R a SiH b Cl c   (II)

wherein R is as defined above,
a=1 to 3,
b=0 to 3,
c=0 to 3, and
a+b+c=4,
with the proviso that at least one silane of the general formula (II) has at least one chlorine substituent at the silicon atom,
to the reaction with one or more metal hydrides selected from the group consisting of an alkali metal hydride and an alkaline earth metal hydride,
in the presence of one or more compounds (C) selected from the group consisting of:
R 1 4 PCl, wherein R 1 is selected from the group consisting of hydrogen and an organyl group, which can be the same or different,
phosphines R 1 3 P, wherein R 1 is selected from the group consisting of hydrogen and an organyl group and can be the same or different,
amines R 1 3 N, wherein R 1 is selected from the group consisting of hydrogen and an organyl group and can be the same or different,
N-heterocyclic amines

Assignees

• Momentive Performance Mat Inc

Inventors

• Auner Norbert
• Santowski Tobias
• Sturm Alexander

Classifications

• C07F7/121

  Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 · CPC title

• C07F7/083 Primary

  Syntheses without formation of a Si-C bond · CPC title

• C07F7/126 Primary

  by reactions involving the formation of Si-Y linkages, where Y is not a carbon or halogen atom · CPC title