Cobalt compound useful as catalyst for hydrosilylation, dehydrogenative silylation and crosslinking of silicone compositions

Patent metadata

Field	Value
Publication number	US-11027267-B2
Application number	US-201716471984-A
Country	US
Kind code	B2
Filing date	Dec 19, 2017
Priority date	Dec 23, 2016
Publication date	Jun 8, 2021
Grant date	Jun 8, 2021

Abstract

The subject of the present invention is the use, as hydrosilylation and/or dehydrogenative silylation catalyst, of a cobalt compound of formula (1): [CO(N(SiR3)2)x]y in which: —the R symbols, which are identical or different, represent a hydrogen atom or a hydrocarbon-based radical having from 1 to 12 carbon atoms, and preferably the R symbols, which are identical or different, are chosen from the group consisting of: a hydrogen atom, alkyl groups having from 1 to 8 carbon atoms and aryl groups having from 6 to 12 carbon atoms, —x=1, 2 or 3 and—y=1 or 2.

First claim

The invention claimed is:

1. A process for preparing hydrosilylation and/or dehydrogenative silylation products by reaction between an unsaturated compound A comprising at least one alkene functional group and/or at least one alkyne functional group with a compound B comprising at least one hydrosilyl functional group, wherein said process is catalyzed by a cobalt compound C of formula (1):
[Co(N(SiR 3 ) 2 ) x ] y   (1)

in which:
the symbols R, which are identical or different, represent a hydrogen atom or a hydrocarbon radical having from 1 to 12 carbon atoms,
x=1, 2 or 3, and
y=1 or 2.

2. The process as claimed in claim 1 , in which the compound C has the formula (2):
[Co(N(SiR 3 ) 2 ) 2 ] y   (2)

in which:
Co represents cobalt with a degree of oxidation of II;
the symbols R, which are identical or different, represent a hydrogen atom or a hydrocarbon radical having from 1 to 12 carbon atoms, and
y=1 or 2.

3. The process as claimed in claim 1 , in which the compound C has the formula (3):
[Co(N(Si(CH 3 ) 3 ) 2 ) 2 ] y   (3)

in which:
Co represents cobalt with a degree of oxidation of II and
y=1 or 2.

4. The process as claimed in claim 1 , carried out in the presence of a compound E of following formula (4):

in which:
A 1 , A 2 , A 3 and A 4 are chosen from: the hydrogen atom, alkyl groups having from 1 to 8 carbon atoms, cycloalkyl groups having from 6 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, halogens, and alkoxy groups of formula OR 1 where R 1 is an alkyl group having from 1 to 8 carbon atoms,
A 5 and A 6 are chosen from: the hydrogen atom, alkyl groups having from 1 to 8 carbon atoms, cycloalkyl groups having from 6 to 12 carbon atoms, and aryl groups having from 6 to 12 carbon atoms, and
A 7 and A 8 are chosen from: alkyl groups having from 1 to 8 carbon atoms, cycloalkyl groups having from 6 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, and alkoxy groups of formula OR 1 where R 1 is an alkyl group having from 1 to 8 carbon atoms.

5. The process as claimed in claim 4 , in which:
A 1 , A 2 , A 3 and A 4 are hydrogen atoms,
A 5 and A 6 are hydrogen atoms,
A 7 and A 8 are chosen from: alkyl groups having from 1 to 8 carbon atoms, cycloalkyl groups having from 6 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, and alkoxy groups of formula OR 1 where R 1 is an alkyl group having from 1 to 8 carbon atoms.

6. The process as claimed in claim 4 , in which the molar ratio of the compound E to cobalt is between 0.5 and 4.

7. The process as claimed in claim 1 , in which the molar concentration of compound C is from 0.01% to 10% with respect to the total number of moles of unsaturations carried by the unsaturated compound A.

8. The process as claimed in claim 1 , wherein said process does not employ compounds based on platinum, palladium, ruthenium or rhodium.

9. The process as claimed in claim 1 , in which the unsaturated compound A comprises from 2 to 40 carbon atoms and one or more alkene or alkyne functional groups.

10. The process as claimed in claim 1 , in which the compound B comprising at least one hydrosilyl functional group is chosen from the group consisting of:
a silane or polysilane compound comprising at least one hydrogen atom bonded to a silicon atom,
an organopolysiloxane compound comprising at least one hydrogen atom bonded to a silicon atom, and
an organic polymer comprising hydrosilyl functional groups in the terminal positions.

11. The process as claimed in claim 1 , in which:
a) the unsaturated compound A is chosen from organopolysiloxane compounds comprising units of formula (I):
Z g U h SiO (4−(g+h))/2   (I)

in which:
the radicals Z, which are identical or different, represent a linear or branched alkenyl or alkynyl radical having from 2 to 6 carbon atoms;
the radicals U, which are identical or different, represent a hydrocarbon radical having from 1 to 12 carbon atoms;
g=1 or 2, h=0, 1 or 2, and g+h=1, 2 or 3;

and optionally comprising other units of formula (II):
U i SiO (4−i)/2   (II)

in which U has the same meaning as above and i=0, 1, 2 or 3, and
b) the compound B is an organopolysiloxane comprising at least one unit of formula (III):
H d U e SiO (4−(d+e))/2   (III)

in which:
the radicals U, which are identical or different, represent a hydrocarbon radical having from 1 to 12 carbon atoms;
d=1 or 2, e=0, 1 or 2, and d+e=1, 2 or 3;

and optionally other units of formula (IV):
U f SiO (4−f)/2   (IV)

in which U has the same meaning as above and f=0, 1, 2 or 3.

12. A product comprising a compound C of formula (1):
[Co(N(SiR 3 ) 2 ) x ] y   (1)

in which:
the symbols R, which are identical or different, represent a hydrogen atom or a hydrocarbon radical having from 1 to 12 carbon atoms,
x=1, 2 or 3, and
y=1 or 2,

in the presence of a compound E of following formula (4):

in which:
A 1 , A 2 , A 3 and A 4 are chosen from: the hydrogen atom, alkyl groups having from 1 to 8 carbon atoms, cycloalkyl groups having from 6 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, halogens, and alkoxy groups of formula OR 1 where R 1 is an alkyl group having from 1 to 8 carbon atoms,
A 5 and A 6 are chosen from: the hydrogen atom, alkyl groups having from 1 to 8 carbon atoms, cycloalkyl groups having from 6 to 12 carbon atoms, and aryl groups having from 6 to 12 carbon atoms, and
A 7 and A 8 are chosen from: alkyl groups having from 1 to 8 carbon atoms, cycloalkyl groups having from 6 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, and alkoxy groups of formula OR 1 where R 1 is an alkyl group having from 1 to 8 carbon atoms

as catalyst for hydrosilylation and/or dehydrogenative silylation between an unsaturated compound A and a compound B comprising at least one hydrosilyl functional group.

13. A composition X comprising:
at least one unsaturated compound A comprising at least one alkene functional group and/or one alkyne functional group,
at least one compound B comprising at least one hydrosilyl functional group, and
a compound C of formula (1):
[Co(N(SiR 3 ) 2 ) x ] y   (1)

in which:
the symbols R, which are identical or different, represent a hydrogen atom or a hydrocarbon radical having from 1 to 12 carbon atoms, and
x=1, 2 or 3, and
y=1 or 2.

14. The composition X as claimed in claim 13 , additionally comprising a compound E of following formula (4):

in which:
A 1 , A 2 , A 3 and A 4 are chosen from: the hydrogen atom, alkyl groups having from 1 to 8 carbon atoms, cycloalkyl groups having from 6 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, halogens, and alkoxy groups of formula OR 1 where R 1 is an alkyl group having from 1 to 8 carbon atoms,
A 5 and A 6 are chosen from: the hydrogen atom, alkyl groups having from 1 to 8 carbon atoms, cycloalkyl groups having from 6 to 12 carbon atoms, and aryl groups having from 6 to 12 carbon atoms, and
A 7 and A 8 are chosen from: alkyl groups having from 1 to 8 carbon atoms, cycloalkyl groups having from 6 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, and alkoxy groups of formula OR 1 where R 1 is an alkyl group having from 1 to 8 carbon atoms.

Assignees

• Elkem Silicones France Sas
• Univ Claude Bernard Lyon
• Centre Nat Rech Scient

Inventors

• Bousquie Magali
• Monteil Vincent
• Raynaud Jean
• Puillet Magali

Classifications

• C08G77/08 Primary

  characterised by the catalysts used · CPC title

• B01J2531/845

  Cobalt · CPC title

• C08K5/5357

  cyclic · CPC title

• C08K5/0091

  Complexes with metal-heteroatom-bonds · CPC title

• C08L83/04 Primary

  Polysiloxanes · CPC title