# US 11,027,267 B2 · Cobalt compound useful as catalyst for hydrosilylation, dehydrogenative silylation and crosslinking of silicone compositions

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 11,027,267 B2
- Document ID: US11027267B2
- Status: Granted
- Kind: B2
- Application number: 16/471,984
- Filed: 2017-12-19
- Published: 2019-10-31
- Granted: 2021-06-08
- Earliest claimed: 2016-12-23
- Assignees: Elkem Silicones France SAS
- Applicants: Elkem Silicones France SAS; Universite Claude Bernard Lyon 1; Centre National De La Recherche Scientifique
- Inventors: Magali Bousquie; Vincent Monteil; Jean Raynaud; Magali Puillet
- Web page: https://patentgrep.com/patent/US11027267B2

## CPC

- B01J 31/1608: {the ligands containing silicon}
- B01J 31/1805: {the ligands containing nitrogen}
- C08G 77/08: characterised by the catalysts used
- C08L 83/04: Polysiloxanes
- B01J 2231/323: Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
- B01J 2531/845: Cobalt
- C08L 2312/08: by silane
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## 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.

## Claims

### Claim 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(SiR3)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.

### Claim 2 (depends on 1)

The process as claimed in claim 1, in which the compound C has the formula (2):
[Co(N(SiR3)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.

### Claim 3 (depends on 1)

The process as claimed in claim 1, in which the compound C has the formula (3):
[Co(N(Si(CH3)3)2)2]y (3)
in which:
Co represents cobalt with a degree of oxidation of II and
y=1 or 2.

### Claim 4 (depends on 1)

The process as claimed in claim 1, carried out in the presence of a compound E of following formula (4):
in which:
A1, A2, A3 and A4 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 OR1 where R1 is an alkyl group having from 1 to 8 carbon atoms,
A5 and A6 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
A7 and A8 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 OR1 where R1 is an alkyl group having from 1 to 8 carbon atoms.

### Claim 5 (depends on 4)

The process as claimed in claim 4, in which:
A1, A2, A3 and A4 are hydrogen atoms,
A5 and A6 are hydrogen atoms,
A7 and A8 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 OR1 where R1 is an alkyl group having from 1 to 8 carbon atoms.

### Claim 6 (depends on 4)

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

### Claim 7 (depends on 1)

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.

### Claim 8 (depends on 1)

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

### Claim 9 (depends on 1)

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.

### Claim 10 (depends on 1)

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.

### Claim 11 (depends on 1)

The process as claimed in claim 1, in which:
a) the unsaturated compound A is chosen from organopolysiloxane compounds comprising units of formula (I):
ZgUhSiO(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):
UiSiO(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):
HdUeSiO(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):
UfSiO(4−f)/2 (IV)
in which U has the same meaning as above and f=0, 1, 2 or 3.

### Claim 12

A product comprising a compound C of formula (1):
[Co(N(SiR3)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:
A1, A2, A3 and A4 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 OR1 where R1 is an alkyl group having from 1 to 8 carbon atoms,
A5 and A6 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
A7 and A8 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 OR1 where R1 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.

### Claim 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(SiR3)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.

### Claim 14 (depends on 13)

The composition X as claimed in claim 13, additionally comprising a compound E of following formula (4):
in which:
A1, A2, A3 and A4 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 OR1 where R1 is an alkyl group having from 1 to 8 carbon atoms,
A5 and A6 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
A7 and A8 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 OR1 where R1 is an alkyl group having from 1 to 8 carbon atoms.

### Claim 15 (depends on 13)

The composition X as claimed in claim 13, comprising:
at least one organopolysiloxane compound A comprising, per molecule, at least two C2-C6 alkenyl radicals bonded to silicon atoms,
at least one organohydropolysiloxane compound B comprising, per molecule, at least two hydrogen atoms bonded to an identical or different silicon atom,
at least one of said compound C, and
optionally at least one compound E of following formula (4):
in which:
A1, A2, A3 and A4 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 OR1 where R1 is an alkyl group having from 1 to 8 carbon atoms,
A5 and A6 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
A7 and A8 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 OR1 where R1 is an alkyl group having from 1 to 8 carbon atoms.

### Claim 16 (depends on 15)

The composition X as claimed in claim 15, in which:
a) the unsaturated compound A is chosen from organopolysiloxane compounds comprising units of formula (I):
ZgUhSiO(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):
UiSiO(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 chosen from organopolysiloxanes comprising at least one unit of formula (III):
HdUeSiO(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):
UfSiO(4−f)/2 (IV)
in which U has the same meaning as above and f=0, 1, 2 or 3.

### Claim 17 (depends on 15)

A crosslinked silicone material Y obtained by heating, to a temperature ranging from 15 to 200° C., a composition X as claimed in claim 15.