# US 10,308,770 B2 · Silicone composition crosslinking catalysts

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- Number: US 10,308,770 B2
- Document ID: US10308770B2
- Status: Granted
- Kind: B2
- Application number: 15/523,494
- Filed: 2015-11-06
- Published: 2018-09-27
- Granted: 2019-06-04
- Earliest claimed: 2014-11-07
- Assignees: Elken Silicones France SAS; Universite Claude Bernard Lyon 1; Centre National De La Recherche Scientifique
- Applicants: Bluestar Silicones France SAS; Universite Claude Bernard Lyon 1; Centre National De La Recherche Scientifique
- Inventors: Vincent Monteil; Jean Raynaud; Delphine Crozet; Magali Bousquié; Sébastien Marrot
- Web page: https://patentgrep.com/patent/US10308770B2

## CPC

- C08G 77/32: Post-polymerisation treatment
- C08G 77/08: characterised by the catalysts used
- C08G 77/12: containing silicon bound to hydrogen
- C08G 77/20: containing silicon bound to unsaturated aliphatic groups
- C08G 77/44: containing only polysiloxane sequences
- C08J 3/24: Crosslinking, e.g. vulcanising, of macromolecules (mechanical aspects B29C35/00; crosslinking agents C08K)
- C08K 3/22: of metals
- C08K 5/0091: {Complexes with metal-heteroatom-bonds}
- C08L 83/00: Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L 83/04: Polysiloxanes
- C08G 77/70: {Siloxanes defined by use of the MDTQ nomenclature}
- C08J 2383/05: containing silicon bound to hydrogen
- C08J 2383/07: containing silicon bound to unsaturated aliphatic groups
- C08J 2483/05: containing silicon bound to hydrogen
- C08J 2483/07: containing silicon bound to unsaturated aliphatic groups
- C08L 2205/025: containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

The invention relates to a crosslinkable composition X, comprising: at least one organopolysiloxane compound A comprising, per molecule, at least two C2-C6 alkenyl radicals bonded to silicon atoms; at least one organohydrogenopolysiloxane compound B comprising, per molecule, at least two hydrogen atoms bonded to an identical or different silicon atom; at least one catalyst C which is a complex corresponding to the following formula: [Fe(L1)2] in which: the symbol Fe represents iron at degree of oxidation II; the symbols L1, which may be identical or different, represent a ligand which is a β-dicarbonylato anion or the enolate anion of a β-dicarbonylated compound; optionally at least one adhesion promoter D; and optionally at least one charge E. The invention also relates to the use of the previously described catalyst C as silicone composition crosslinking catalyst, to a silicone composition crosslinking method, wherein it comprises heating the composition X to a temperature of between 70 and 200° C., and to the resulting crosslinked silicone material Y.

## Claims

### Claim 1

A crosslinkable composition X comprising:
at least one organopolysiloxane compound A comprising, per molecule, at least two C2-C6 alkenyl radicals bonded to silicon atoms,
at least one organohydrogenopolysiloxane compound B comprising, per molecule, at least two hydrogen atoms bonded to an identical or different silicon atom,
at least one catalyst C which is a complex corresponding to the following formula:
[Fe(L1)2]
in which:
the symbol Fe represents iron in oxidation state II,
the symbols L1, which may be identical or different, represent a ligand which is a β-dicarbonylato anion or the enolate anion of a β-dicarbonyl compound,
optionally at least one adhesion promoter D and
optionally at least one filler E,
wherein said composition is free of any catalysts comprising rhodium.

### Claim 2 (depends on 1)

The composition X as claimed in claim 1, wherein the catalyst C is present in a content ranging from 0.001 to 10 mol % of iron per number of moles of C2-C6 alkenyl radicals bonded to silicon atoms in the organopolysiloxane compound A.

### Claim 3 (depends on 1)

The composition X claimed in claim 1, wherein said composition is free of catalyst based on any of platinum, palladium, ruthenium or rhodium.

### Claim 4 (depends on 1)

The composition X as claimed in claim 1, wherein the ligand L1 is an anion derived from a compound of formula (1):
R1COCHR2COR3 (1)
in which:
R1 and R3, which may be identical or different, represent a linear, cyclic or branched C1-C30 hydrocarbon-based radical, an aryl containing between 6 and 12 carbon atoms or a radical
OR4 with R4 representing a linear, cyclic or branched C1-C30 hydrocarbon-based radical,
R2 is a hydrogen atom or a hydrocarbon-based radical; wherein
R1 and R2 may be joined together to form a C5-C6 ring, and
R2 and R4 may be joined together to form a C5-C6 ring.

### Claim 5 (depends on 4)

The composition X as claimed in claim 4, in which the compound of formula (1) is chosen from the group formed by the following β-diketones: 2,4-pentanedione (acac); 2,4-hexanedione; 2,4-heptanedione; 3,5-heptanedione; 3-ethyl-2,4-pentanedione; 5-methyl-2,4-hexanedione; 2,4-octanedione; 3,5-octanedione; 5,5-dimethyl-2,4-hexanedione; 6-methyl-2,4-heptanedione; 2,2-dimethyl-3,5-nonanedione; 2,6-dimethyl-3,5-heptanedione; 2-acetylcyclohexanone (Cy-acac); 2,2,6,6-tetramethyl-3,5-heptanedione (TMHD); 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (F-acac); benzoylacetone; dibenzoylmethane; 3-methyl-2,4-pentadione; 3-acetyl-2-pentanone; 3-acetyl-2-hexanone; 3-acetyl-2-heptanone; 3-acetyl-5-methyl-2-hexanone; benzoylstearoylmethane; benzoylpalmitoylmethane; octanoylbenzoylmethane; 4-t-butyl-4′-methoxydibenzoylmethane; 4,4′-dimethoxydibenzoylmethane and 4,4′-di-tert-butyldibenzoylmethane.

### Claim 6 (depends on 4)

The composition X as claimed in claim 4, in which the compound of formula (1) is chosen from the group formed from the β-diketones 2,4-pentanedione (acac) or 2,2,6,6-tetramethyl-3,5-heptanedione (TMHD).

### Claim 7 (depends on 1)

The composition X as claimed in claim 1, in which the catalyst C is chosen from the complexes [Fe(acac)2] and [Fe(TMIHD)2].

### Claim 8 (depends on 1)

The composition X as claimed in claim 1, wherein the organopolysiloxane A comprises:
(i) at least two siloxyl units (A.1), which may be identical or different, having the following formula:
W
a
⁢
Z
b
⁢
SiO
4
-
(
a
+
b
)
2
(
A
⁢
.1
)
in which:
a=1 or 2, b=0, 1 or 2 and a+b=1, 2 or 3;
the symbols W, which may be identical or different, represent a linear or branched C2-C6 alkenyl group,
and the symbols Z, which may be identical or different, represent a monovalent hydrocarbon-based group containing from 1 to 30 carbon atoms,
(ii) and optionally at least one siloxyl unit having the following formula:
Z
a
1
⁢
SiO
4
-
a
2
(
A
⁢
.2
)
in which:
a=0, 1, 2 or 3,
the symbols Z′, which may be identical or different, represent a monovalent hydrocarbon-based group containing from 1 to 30 carbon atoms.

### Claim 9 (depends on 1)

The composition X as claimed in claim 1, in which the organohydrogenopolysiloxane compound B comprises at least three hydrogen atoms per molecule directly bonded to an identical or different silicon atom.

### Claim 10 (depends on 1)

The composition X as claimed in claim 1, in which the organohydrogenopolysiloxane compound B is an organopolysiloxane comprising:
(i) at least two siloxyl units having the following formula:
H
d
⁢
Z
e
3
⁢
SiO
4
-
(
d
+
e
)
2
(
B
⁢
.1
)
in which:
d=1 or 2, e=0, 1 or 2 and d+e=1, 2 or 3,
the symbols Z3, which may be identical or different, represent a monovalent hydrocarbon-based group containing from 1 to 30 carbon atoms and
(ii) optionally at least one siloxyl unit having the following formula:
Z
c
2
⁢
SiO
4
-
c
2
(
B
⁢
.2
)
in which:
c=0, 1, 2 or 3,
the symbols Z2, which may be identical or different, represent a monovalent hydrocarbon-based group containing from 1 to 30 carbon atoms.

### Claim 11 (depends on 1)

The composition X as claimed in claim 1, wherein said composition comprises a second organopolysiloxane compound comprising, per molecule, at least two C2-C6 alkenyl radicals bonded to silicon atoms, different from the organopolysiloxane compound AI.

### Claim 12 (depends on 1)

The composition X as claimed in claim 1, wherein proportions of the organopolysiloxane A and of the organohydrogenopolysiloxane B are such that the mole ratio of hydrogen atoms bonded to silicon in the organohydrogenopolysiloxane B to the alkenyl radicals bonded to silicon in the organopolysiloxane A is between 0.2 and 20.

### Claim 13 (depends on 1)

The composition X as claimed in claim 1, wherein said composition comprises one or more functional additives chosen from:
silicone resins,
adhesion modifiers,
consistency-enhancing additives,
pigments, and
heat-resistance, oil-resistance or fire-resistance additives, optionally metal oxides.

### Claim 14 (depends on 1)

A process for crosslinking one or more silicone compositions, wherein said process comprises heating a composition X as claimed in claim 1 to a temperature ranging from 70 to 200° C.

### Claim 15 (depends on 1)

A crosslinked silicone material Y obtained by heating to a temperature ranging from 70 to 200° C., a composition X as claimed in claim 1.

### Claim 16 (depends on 1)

The composition X as claimed in claim 1, wherein said composition comprises a second organopolysiloxane compound which is a divinyltetramethyl disiloxane.

### Claim 17

A silicone composition product crosslinked with a catalyst C, which is a complex corresponding to the following formula:
[Fe(L1)2]
in which:
the symbol Fe represents iron in oxidation state II,
the symbols L1, which may be identical or different, represent a ligand which is a β-dicarbonylato anion or the enolate anion of a β-dicarbonyl compound, wherein said composition is not crosslinked with any catalysts comprising rhodium.