Method for oligomerizing hydridosilanes, the oligomers that can be produced by means of the method, and the use thereof

Patent metadata

Field	Value
Publication number	US-8969610-B2
Application number	US-201113574376-A
Country	US
Kind code	B2
Filing date	Feb 16, 2011
Priority date	Feb 26, 2010
Publication date	Mar 3, 2015
Grant date	Mar 3, 2015

Abstract

The present invention relates to a method for oligomerizing hydridosilanes, wherein a composition comprising substantially at least one non-cyclic hydridosilane having a maximum of 20 silicon atoms as the hydridosilane is thermally converted at temperatures below 235° C. in the absence of a catalyst, the oligomers that can be produced according to the method, and the use thereof.

First claim

The invention claimed is:

1. A process for oligomerizing a hydridosilane, the process comprising:
thermally converting, in the absence of a catalyst, a composition comprising a noncyclic hydridosilane comprising a maximum of 20 silicon atoms at a temperature of less than 235° C.

2. The process of claim 1 , being a liquid phase process.

3. The process of claim 1 , wherein the composition comprises a hydridosilane mixture having a weight-average molecular weight, M w , of ≦500 g/mol.

4. The process of claim 1 , further comprising, prior to the thermal conversion:
(A) converting a first mixture comprising: i) a halosilane having formula Si n X 2n+2 , wherein n≧3, and X is at least one selected from the group consisting of F, Cl, Br, and I; and ii) a catalyst having formula:
NRR′ a R′ b Y c ,

wherein:
a=0 or 1, b=0 or 1 and c=0 or 1; and

where
aa)—at least one selected from the group consisting of R, R′, and R″ is a —C 1 -C 12 -alkyl, a —C 1 -C 12 -aryl, a —C 1 -C 12 -aralkyl, a —C 1 -C 12 -aminoalkyl, a —C 1 -C 12 -aminoaryl, a —C 1 -C 12 -aminoaralkyl,
and/or
two or three R, R′, and R″ radicals, in the case that c=0, together form a cyclic or bicyclic, heteroaliphatic or heteroaromatic system comprising N,
with the proviso that at least one of the R, R′, or R″ radical is not —CH 3 , and/or

bb) at least one selected from the group consisting of (i) R and R′ and (ii) R″ (in the case that c=1) is a —C 1 -C 12 -alkylene, a —C 1 -C 12 -arylene, a —C 1 -C 12 -aralkylene, a —C 1 -C 12 -heteroalkylene, a —C 1 -C 12 -heteroarylene, a —C 1 -C 12 -heteroaralkylene, —N═, or any mixture thereof,
or
cc) in the case that a=b=c=0, R═≡C—R′″, wherein R′″=a —C 1 -C 10 -alkyl, a —C 1 -C 10 -aryl, a —C 1 -C 10 -aralkyl, or any mixture thereof, to form a second mixture comprising a halosilane of formula Si m X 2m+2 , wherein m>n and X is at least one selected from the group consisting of F, Cl, Br, and I; and SiX 4 wherein X is at least one selected from the group consisting of F, Cl, Br, and I; and then
(B) hydrogenating the halosilane of formula Si m X 2m+2 , to form a hydridosilane of having formula Si m H 2m+2 .

5. The process of claim 1 , wherein the composition comprises neopentasilane.

6. The process of claim 1 , wherein the composition further comprises at least one solvent selected from the group consisting of a linear, branched and cyclic, saturated, unsaturated and aromatic hydrocarbon comprising 1 to 12 carbon atoms, an alcohol, an ether, a carboxylic acid, an ester, a nitrile, an amine, an amide, a sulphoxide, and water.

7. The process of claim 1 , wherein the composition further comprises 20-80% by weight of a solvent, based on a total mass of the composition.

8. The process of claim 1 , wherein the composition further comprises at least one dopant selected from the group consisting of:
BH x R 3-x , wherein x=0-3 and R=a C 1 -C 10 -alkyl radical, unsaturated cyclic, optionally ether- or amino-complexed C 2 -C 10 -alkyl radical;
Si 5 H 9 BR 2 , wherein R═H, Ph, or a C 1 -C 10 -alkyl radical;
Si 4 H 9 BR 2 , wherein R═H, Ph, or a C 1 -C 10 -alkyl radical;
red phosphorus;
white phosphorus (P 4 );
PH x R 3-x , wherein x=0-3 and R=Ph, SiMe 3 , or a C 1 -C 10 -alkyl radical;
P 7 (SiR 3 ) 3 , wherein R═H, Ph, or a C 1 -C 10 -alkyl radical;
Si 5 H 9 PR 2 , wherein R═H, Ph, or a C 1 -C 10 -alkyl radical; and
Si 4 H 9 PR 2 , wherein R═H, Ph, or a C 1 -C 10 -alkyl radical.

9. The process of claim 8 , wherein a content of the dopant in the composition is from 0.01-20% by weight, based on total mass of the composition.

10. The process of claim 1 , further comprising, during the thermal conversion or thereafter:
adding a dopant to the composition, wherein the dopant is at least one selected from the group consisting of:
BH x R 3-x , wherein x=0-3 and R=a C 1 -C 10 -alkyl radical, unsaturated cyclic, optionally ether- or amino-complexed C 2 -C 10 -alkyl radical;
Si 5 H 9 BR 2 , wherein R═H, Ph, or a C 1 -C 10 -alkyl radical;
Si 4 H 9 BR 2 , wherein R═H, Ph, or a C 1 -C 10 -alkyl radical;
red phosphorus;
white phosphorus (P 4 );
PH x R 3-x , wherein x=0-3 and R=Ph, SiMe 3 , or a C 1 -C 10 -alkyl radical;
P 7 (SiR 3 ) 3 , wherein R═H, Ph, or a C 1 -C 10 -alkyl radical;
Si 5 H 9 PR 2 , wherein R═H, Ph, or a C 1 -C 10 -alkyl radical; and
Si 4 H 9 PR 2 , wherein R═H, Ph, or a C 1 -C 10 -alkyl radical.

11. The process of claim 1 , wherein the thermal conversion is performed at a temperature in the range from 70 to 220° C.

12. The process of claim 1 , wherein the composition comprises a hydridosilane mixture having a weight-average molecular weight, M w , of ≦400 g/mol.

13. The process of claim 1 , wherein the composition comprises a hydridosilane mixture having a weight-average molecular weight, M w , of ≦350 g/mol.

14. The process of claim 1 , wherein the noncylic hydridosilane consist essentially of neopentasilane.

15. The process of claim 1 , wherein the thermal conversion is performed at a temperature in the range from 90 to 210° C.

Assignees

• Wieber Stephan
• Patz Matthias
• Stuetzel Bernhard
• Coelle Michael
• Brausch Nicole
• Klatt Janette
• Hessing Jutta
• Evonik Degussa Gmbh

Inventors

• Wieber Stephan
• Patz Matthias
• Stuetzel Bernhard
• Coelle Michael
• Brausch Nicole
• Klatt Janette
• Hessing Jutta

Classifications

• H10P14/3411

  Silicon, silicon germanium or germanium · CPC title

• H10P14/2922

  being non-crystalline insulating materials, e.g. glass or polymers · CPC title

• H10P14/265

  using solutions · CPC title

• C08G77/60 Primary

  in which all the silicon atoms are connected by linkages other than oxygen atoms · CPC title

• C09D183/16

  in which all the silicon atoms are connected by linkages other than oxygen atoms · CPC title