Integrated process for the manufacture of methylchlorohydridomonosilanes

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).