Integrated process for the manufacture of methylchlorohydridomonosilanes

Patent metadata

Field	Value
Publication number	US-11518773-B2
Application number	US-201816647573-A
Country	US
Kind code	B2
Filing date	Sep 20, 2018
Priority date	Sep 20, 2017
Publication date	Dec 6, 2022
Grant date	Dec 6, 2022

Abstract

The present invention relates to an integrated process for the manufacture of methylchlorohydridomonosilanes in particular, from products of the Müller-Rochow Direct Process.

First claim

The invention claimed is:

1. A process for the manufacture of methylchlorohydridomonosilanes, selected from the group consisting of Me 2 Si(H)Cl, MeSi(H)Cl 2 , and MeSi(H) 2 Cl, comprising:
subjecting a silane substrate comprising at least one silane selected from the group consisting of:
(i) monosilanes,
(ii) disilanes,
(iii) oligosilanes, and
(iv) carbodisilanes,
with the proviso that the at least one silane (i) to (iv) has at least one chloro substituent,

a) to a hydrogenation reaction with LiH, and
b) to a redistribution reaction, and
c) optionally to a cleavage reaction of the Si—Si bonds of the di- or oligosilanes or the Si—C-bond of the carbodisilanes, and
d) to a separating step of the methylchlorohydridosilanes,
wherein the process is carried out in the presence of an ether solvent having a boiling point of greater than 70° C., in the absence of AlCl 3 , and wherein
(i) the monosilanes are selected from the group consisting of the general formula (I),
Me x SiH y Cl z   (I),

wherein
x=1 to 3,
y=0 to 3,
z=0 to 3, and
x+y+z=4,

(ii) the disilanes are selected from the group consisting of the general empirical formula (II),
Me m Si 2 H n Cl o   (II)

wherein
m=1 to 6,
n=0 to 5
o=0 to 5 and
m+n+o=6,

(iii) oligosilanes are selected from the group consisting of linear or branched oligosilanes of the general empirical formula (III)
Me p Si q H r Cl s   (III),

wherein
q=3-7
p=q to (2q+2)
r, s=0 to (q+2)
r+s=(2q+2)−p,

(iv) carbodisilanes are selected from the group consisting of the general formula (IV)
(Me a SiH b Cl e )—CH 2 -(Me c SiH d Cl f )  (IV)

wherein
a, c are independently of each other 1 to 3,
b, d are independently from each other 0 to 2
e, f are independently from each other 0 to 2,
a+b+e=3,
c+d+f=3 and,

wherein the process further comprises the step of separating the LiCl formed and the step of regeneration of LiH from the separated LiCl, and wherein the process is conducted at a temperature of from about −40° C. to about 250° C. and wherein the hydrogenation reaction a), the redistribution reaction b) and the cleavage reaction c) are carried out simultaneously.

2. A process according to claim 1 , wherein the silane substrate is consists of:
(i) monosilanes,
(ii) disilanes,
(iii) oligosilanes, or
(iv) carbodisilanes.

3. The process of claim 1 , wherein
(i) the monosilanes are selected from the group consisting of formulas:
MeSiCl 3 , Me 2 SiCl 2 , Me 3 SiCl, MeSiHCl 2 , Me 2 SiHCl, MeSiH 2 Cl, MeSiH 3 , Me 2 SiH 2 and Me 3 SiH,
(ii) the disilanes are selected from the group consisting of formulas:
Cl 2 MeSi—SiMeCl 2 , Cl 2 MeSi—SiMe 2 Cl, Cl 2 MeSi—SiMe 3 ClMe 2 Si—SiMe 2 Cl, Me 3 Si—SiMe 2 Cl, HMe 2 Si—SiMe 2 Cl, H 2 MeSi—SiMeClH, HClMeSi—SiMeClH, ClHMeSi—SiMeCl 2 , H 2 MeSi—SiMeCl 2 , HMe 2 Si—SiMeCl 2 , ClMe 2 Si—SiMeH 2 , HMe 2 Si—SiMeClH, ClMe 2 Si—SiMeClH, Me 3 Si—SiMeClH, HMe 2 Si—SiMe 2 H, H 2 MeSi—SiMeH 2 , HMe 2 Si—SiMeH 2 , Me 3 Si—SiMeH 2 and Me 3 Si—SiMe 2 H,
(iii) oligosilanes are selected from the group consisting of formulas:
ClMe 2 Si—SiMe 2 -SiMe 2 Cl, ClMe 2 Si—SiMe 2 -SiMe 2 -SiMe 2 Cl, (ClMe 2 Si) 3 SiMe, (Cl 2 MeSi) 2 SiMeCl, (Cl 2 MeSi) 3 SiMe, (Cl 2 MeSi) 2 SiMe-SiClMe-SiCl 2 Me, [(Cl 2 MeSi) 2 SiMe] 2 , [(Cl 2 MeSi) 2 SiMe] 2 SiClMe, (Cl 2 MeSi) 2 SiMe-SiMe 2 Cl, ClMe 2 Si—SiMe 2 SiMe 2 H, HMe 2 Si—SiMe 2 -SiMe 2 H, HMe 2 Si—SiMe 2 -SiMe 2 -SiMe 2 H, (HMe 2 Si) 3 SiMe, (H 2 MeSi) 2 SiMeH, (H 2 MeSi) 3 SiMe, (H2MeSi)2SiMe-SiHMe-SiH2Me, [(H2MeSi)2SiMe]2, [(H2MeSi)2SiMe]2SiHMe and (H2MeSi)2SiMe-SiMe2H,
(iv) the carbodisilanes are selected from the group consisting of formulas:
Cl 2 MeSi—CH 2 —SiMeCl 2 , ClMe 2 Si—CH 2 —SiMeCl 2 , ClMe 2 Si—CH 2 —SiMe 2 Cl, Me 3 Si—CH 2 —SiMeCl 2 Me 3 Si—CH 2 —SiMe 2 Cl, HClMeSi—CH 2 —SiMeClH, HMe 2 Si—CH 2 —SiMeCl 2 , HMe 2 Si—CH 2 —SiMe 2 Cl, Me 3 Si—CH 2 —SiMeClH, H 2 MeSi—CH 2 —SiMeH 2 , HMe 2 Si—CH 2 —SiMeH 2 , HMe 2 Si—CH 2 —SiMe 2 H, Me 3 Si—CH 2 —SiMeH 2 , and Me 3 Si—CH 2 —SiMe 2 H,

with the proviso that at least one of the silanes used in the process has at least one chloro substituent.

4. The process of claim 1 , wherein the silane substrate comprises at least one silane selected from the group consisting of MeSiCl 3 , Me 2 SiCl 2 , Me 3 SiCl, MeSiHCl 2 , Me 2 SiHCl, MeSiH 2 Cl, MeSiH 3 , Me 2 SiH 2 , Me 3 SiH, Cl 2 MeSi—SiMeCl 2 , Cl 2 MeSi—SiMe 2 Cl, Cl 2 MeSi—SiMe 3 , ClMe 2 Si—SiMe 2 Cl, Me 3 Si—SiMe 2 Cl, Cl 2 MeSi—CH 2 —SiMeCl 2 , ClMe 2 Si—CH 2 —SiMeCl 2 , ClMe 2 Si—CH 2 —SiMe 2 Cl, Me 3 Si—CH 2 —SiMeCl 2 and Me 3 Si—CH 2 —SiMe 2 Cl.

5. The process of claim 1 , wherein the redistribution reaction of silanes comprises the comproportionation of two different methylsilanes, leading to the formation of one specific chlorohydridomethylsilane.

6. The process of claim 1 , wherein the redistribution reaction b) is carried out in the presence of at least one redistribution catalyst.

7. The process of claim 1 , wherein the cleavage reaction c) is carried out in the presence of at least one cleavage catalyst.

8. The process of claim 1 , wherein the silane substrate comprises a product of the Müller-Rochow Direct Process.

9. The process, of claim 1 , wherein the silane substrate comprises the entire product of the Müller-Rochow Direct Process or a part (fraction) of the product of the Müller-Rochow Direct Process.

10. The process of claim 1 , wherein the silane substrate comprises the monosilane fraction of the Müller-Rochow Direct Process product.

11. The process, of claim 1 , wherein the silane substrate is the higher silane fraction (silanes having ≥2 Si atoms) of the Müller-Rochow Direct Process product.

12. The process of claim 6 , wherein the redistribution catalyst is selected from the group consisting of:
R 4 PCl, wherein R is hydrogen or an organyl group, which can be the same or different,
triorganophosphines, wherein R is hydrogen or an organyl group,
triorganoamines, wherein R is an organyl group,
N-heterocyclic amines,
quaternary ammonium compounds,
an alkali metal halide,
an alkaline earth metal halide,
an alkali metal hydride, and
an alkaline earth metal hydride.

13. The process of claim 6 , wherein the cleavage catalyst is selected from the group consisting of:
a quaternary Group 15 onium compound R 4 QX, wherein each R is independently a hydrogen or an organyl group, Q is phosphorus, arsenic, antimony or bismuth, and X is a halide selected from the group consisting of F, Cl, Br and I,
a heterocyclic amine,
a heterocyclic ammonium halide,
a mixture of R 3 P and RX,

wherein R is as defined above, and X is as defined above,
alkali metal halide,
an alkaline earth metal halide,
an alkali metal hydride,
alkaline earth metal hydride or mixtures thereof, optionally in the presence of hydrogen chloride (HCl).

Assignees

• Momentive Performance Mat Inc

Inventors

• Auner Norbert
• Santowski Tobias
• Sturm Alexander
• Felder Thorsten
• Lewis Kenrick

Classifications

• Y02P20/10

  Process efficiency · CPC title

• C07F7/14 Primary

  Preparation thereof from {optionally substituted} halogenated silanes and hydrocarbons {hydrosilylation reactions} · 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