# US 8,772,428 B2 · RTV-organopolysiloxane compositions and novel organopolysiloxane polycondensation catalysts therefor

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- Number: US 8,772,428 B2
- Document ID: US8772428B2
- Status: Granted
- Kind: B2
- Application number: 12/808,744
- Filed: 2008-12-18
- Published: 2011-01-27
- Granted: 2014-07-08
- Earliest claimed: 2007-12-20
- Assignees: Bluestar Silicones France SAS
- Applicants: Christian Maliverney; Delphine Blanc; Rachid Ferhat
- Inventors: Christian Maliverney; Delphine Blanc; Rachid Ferhat
- Web page: https://patentgrep.com/patent/US8772428B2

## CPC

- C08L 83/04: Polysiloxanes
- C08K 5/0091: {Complexes with metal-heteroatom-bonds}
- C08G 77/16: to hydroxy groups
- C08K 5/56: Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

RTV-organopolysiloxane compositions are crosslinkable by polycondensation and are devoid of alkyltin-based catalysts; novel organopolysiloxane polycondensation catalysts are useful therefor.

## Claims

### Claim 1

An RTV-organopolysiloxane composition comprising a silicone base B capable of curing via polycondensation reaction into a silicone elastomer and a catalytically effective amount of at least one catalyst system X,
wherein the catalyst system X comprises a milled homogeneous mixture of at least one metal complex or salt A dispersed in at least one oily organopolysiloxane polymer K having a viscosity of at least 100 mPa·s, and,
wherein the at least one metal complex or salt A has formula (1) below:
[M(L1)r1(L2)r2(Y)x] (1)
in which:
r1≧1, r2≧0 and x≧0;
the symbol M is a metal selected from the group consisting of copper, silver, iron, boron, scandium, cerium, ytterbium, bismuth, molybdenum, germanium and manganese;
the symbol L1 is a ligand which is a β-dicarbonylato anion or the enolate anion of a β-dicarbonyl-containing compound and when r1≧2, the symbols L1 are identical or different;
the symbol L2 is an anionic ligand which is different from L1 and when r2≧2, the symbols L2 are identical or different; and
the symbol Y is a neutral ligand and when x≧2, the symbols Y are identical or different.

### Claim 2 (depends on 1)

The RTV-organopolysiloxane composition as defined by claim 1, wherein the milling is carried out by means of a 3-roll mill, the clamping pressures of which, from the rolls, are adjusted so as to result in a homogeneous mixture.

### Claim 3 (depends on 1)

The RTV-organopolysiloxane composition as defined by claim 1, wherein the catalyst system X comprises at least one metal complex or salt A of formula (2) below:
[M (L1)r1(L2)r2] (2)
in which:
r1≧1 and r2≧0;
the symbol is a metal selected from the group consisting of copper, silver, iron, boron, scandium, cerium, ytterbium, bismuth, molybdenum, germanium and manganese;
the symbol L1 is a ligand which is a β-dicarbonylato anion or the enolate anion of a β-dicarbonyl-containing compound and when r1≧2, the symbols L1 are identical or different; and
the symbol L2 is an anionic ligand which is different from L1 and when r2≧2, the symbols L2 are identical or different.

### Claim 4 (depends on 1)

The RTV-organopolysiloxane composition as defined by claim 1, wherein the catalyst system X comprises at least one metal complex or salt A selected from the group consisting of the metal complexes or salts of formulae (3) to (7) below:
[Ce(L1)r3(L2)r4]; where r3≧1 and r4≧0 and r3+r4=3; (3)
[Mo(L1)r5(L2)r6]; where r5≧1 and r6≧0 and r5+r6=6; (4)
[Bi(L1)r7(L2)r8]; where r7≧1 and r8≧0 and r7+r8=3; (5)
[Mn(L1)r9(L2)r10]; where r9≧1 and r10≧0 and r9+r10=3; (6)
[Fe(L1)r11(L2)r12]; where r11≧1 and r12≧0 and r11+r12=3; (7)
in which:
the symbol L1 is a ligand which is a β-dicarbonylato anion or the enolate anion of a β-dicarbonyl-containing compound and when the number of ligands L1≧2, the symbols L1 are identical or different; and
the symbol L2 is an anionic ligand which is different from L1 and when the number of ligands L2≧2, the symbols L2 are identical or different.

### Claim 5 (depends on 4)

The RTV-organcpolysiloxane composition as defined by claim 4, wherein the catalyst system X comprises at least one metal complex or salt A selected from the group consisting of the metal complexes and salts of formulae (8)-(27) and (32)-(33) below:
[Ce(t-Bu-acac)3] where (t-Bu-acac)=the 2,2,6,6-tetramethyl-3,5-heptanedionato anion or the enolate anion of 2,2,6,6-tetramethyl-3,5-heptanedione; (8)
[Ce(acac)3] where acac=the 2,4-pentanedionato anion or the enolate anion of 2,4-pentanedione; (9)
[Ce(EAA)3] where EAA=the ethyl acetoacetato anion or the enolate anion of ethyl acetoacetate; (10)
[Mo(O2)(t-Bu-acac)2] where (t-Bu-acac)=the 2,2,6,6-tetramethyl-3,5-heptanedionato anion or the enolate anion of 2,2,6,6-tetramethyl-3,5-heptanedione; (11)
[Mo(O2)(Cy-acac)2] where Cy-acac=the 2-acetylcyclohexanonato anion or the enolate anion of 2-acetylcyclohexanone; (12)
[Mo(O2)(acac)2] where acac=the 2,4-pentanedionato anion or the enolate anion of 2,4-pentanedione; (13)
[Mo(O2)(Cp-acac)2] where Cp-acac=the 2-acetylcyclopentanonato anion or the enolate anion of 2-acetylcyclopentanone; (14)
[Mn(acac)3] where acac=the 2,4-pentanedionato anion or the enolate anion of 2,4-pentanedione; (15)
[Fe(t-Bu-acac)3] where (t-Bu-acac)=the 2,2,6,6-tetramethyl-3,5-heptanedionato anion or the enolate anion of 2,2,6,6-tetramethyl-3,5-heptanedione; (16)
[Fe(EAA)3] where EAA=the ethyl acetoacetato anion or the enolate anion of ethyl acetoacetate; (17)
[Fe(EAA)2(2-ethylhexanoato)] where EAA=the ethyl acetoacetato anion or the enolate anion of ethyl acetoacetate; (18)
[Fe(EAA)(2-ethylhexanoato)2] where EAA=the ethyl acetoacetato anion or the enolate anion of ethyl acetoacetate; (19)
[Fe(acac)3] where acac=the 2,4-pentanedionato anion or the enolate anion of 2,4-pentanedione; (20)
[Fe(trifluoro-acac)3] where trifluoro-acac=the trifluoroacetylacetonato anion; (21)
[Fe(iPr-AA)3] where iPr-AA=the isopropyl acetoacetato anion or the enolate anion of isopropyl acetoacetate; (22)
[Fe(iBu-AA)3] where iPr-AA=the isobutyl acetoacetato anion or the enolate anion of isobutyl acetoacetate; (23)
[Fe(tBu-AA)3] where tPr-AA=the tert-butyl acetoacetato anion or the enolate anion of tert-butyl acetoacetate; (24)
[Bi(hfacac)3] where hfacac=the 1,1,1,5,5,5-hexafluoropentanedionato anion; (27)
[Fe(isopropyl acetoacetato)2(2,2-dimethylbutyrato)]; and (32)
[Fe(isopropyl acetoacetato)(2,2-dimethylbutyrato)2]. (33)

### Claim 6 (depends on 1)

The RTS-organopolysiloxane composition as defined by claim 1, wherein the β-dicarbonylato ligand L1 is a β-diketonato anion derived from a β-diketone or a β-ketoesterato anion derived from a β-keto ester of the following formula:
R1COCHR2COR3 (34)
in which:
R1 is a substituted or unsubstituted, linear or branched C1-C30 hydrocarbon-based radical or a substituted or unsubstituted aromatic radical;
R2 is a hydrogen or a hydrocarbon-based radical having at most 4 carbon atoms;
R3 is a substituted or unsubstituted, linear; cyclic or branched C1-C30 hydrocarbon-based radical, a substituted or unsubstituted aromatic radical, or an —OR4 radical wherein R4 is a substituted cr unsubstituted, linear, cyclic or branched C1-C30 hydrocarbon-based radical;
wherein,
R1 and R2 may be joined together to form a ring member; and
R2 and R4 may be joined together to form a ring member.

### Claim 7 (depends on 6)

The RTV-organopolysiloxane composition as defined by claim 6, wherein the β-diketone of formula (34) is selected from the group consisting of 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 (t-Bu-acac); 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; stearoyl benzoyl methane; octanoyl benzoyl methane; 4-t-butyl-4′-methoxydibenzoylmethane; 4,4′-dimethoxydibenzoylmethane and 4,4′-di-tart-butyldibenzoylmethane.

### Claim 8 (depends on 1)

The RTV-organopolysiloxane composition as defined by claim 1, wherein L2 is an anionic ligand selected from the group consisting of the following anions: fluoro (F−), chloro (Cl−), triiodo(1−) (I3)−, difluorochlorato(1−) [CIF2]−, hexafluoroiodato(1−) [IF6]−, oxochlorato(1−) (ClO)−, dioxochlorato(1−) (ClO2)−, trioxochlorato(1−) (ClO3)−, tetraoxochlorato(1−) (ClO4)−, hydroxo (OH)−, mercapto (SH)−, selanido (SeH)−, hyperoxo (O2)−, ozonido (O3)−, hydroxo (OH−), hydrodisulfido (HS2)−, methoxo (CH3O)−, ethoxo (C2H5O)−, propoxido (C3H7O)−, methylthio (CH3S)−, ethanethiolato (C2H5S)−, 2-chloroethanolato (C2H4ClO)−, phenoxido (C6H5O)−, phenylthio (C6H5S)−, 4-nitrophenolato [C6H4(NO2)O]−, formato (HCO2)−, acetato (CH3CO2)−, propionato (CH3CH2CO2)−, nitrido (N3)−, cyano (CN)−, cyanato (NCO)−, thiocyanato (NCS)−, selenocyanato (NCSe)−, amido (NH2)−, phosphino (PH2)−, chloroazanido (ClHN)−, dichloroazanido (Cl2N)−, [methanaminato(1−)] (CH3NH)−, diazenido (HN═N)−, diazanido (H2N—NH)−, diphosphenido (HP═P)−, phosphonito (H2PO)−, phosphinato (H2PO2)−, carboxylato, enolato, amides, alkylato and arylato.

### Claim 9 (depends on 1)

The RTV-organopolysiloxane composition as defined by claim 1, wherein L2 is an anionic ligand selected from the group consisting of the following anions: acetate, oxalate, propionate, butyrate, isobutyrate, diethylacetate, benzoate, 2-ethylhexanoate, stearate, methoxide, ethoxide, isopropoxide, tert-butoxide, tert-pentoxide, 8-hydroxyquinolinate, naphthenate, tropolonate and the oxido O2− anion.

### Claim 10 (depends on 1)

The RTV-organopolysiloxane composition as defined by claim 1, comprising a catalytically effective amount of at least one catalyst system X and a silicone base B which comprises:
at least one polyorganosiloxane oil C capable of crosslinking via polycondensation into an elastomer;
optionally, at least one crosslinking agent D;
optionally, at least one adhesion promoter E; and
optionally, at least one siliceous, organic and/or non-siliceous mineral filler F.

### Claim 11 (depends on 10)

A two-component system that is a precursor of the RTV-organopolysiloxane composition as defined by claim 10, comprising two separate parts P1 and P2 to be mixed to form said composition, and wherein one of these parts comprises the catalyst system X as a catalyst for the polycondensation reaction of organopolysiloxanes and the crosslinking agent D, and further wherein the other part is free of the aforesaid species and comprises:
per 100 parts by weight of the polyorganosiloxane oil(s) C capable of crosslinking via polycondensation into an elastomer; and
from 0.001 to 10 part(s) by weight of water.

### Claim 12 (depends on 1)

A single-component polyorganosiloxane composition that is stable during storage in the absence of moisture and that crosslinks, in the presence of water, into an elastomer, which comprises:
at least one crosslinkable linear polyorganopolysiloxane that has functionalized alkoxy, oxime, acyl and/or enoxy ends, type;
a filler; and
the catalyst system X as defined by claim 1.

### Claim 13 (depends on 10)

The RTV-organopolysiloxane composition as defined by claim 10, wherein the composition comprises,
(a) the silicone base B comprising:
per 100 parts by weight of at least one polyorganosiloxane oil C capable of crosslinking via polycondensation, which is a reactive α,ω-dihydroxydiorganopolysiloxane polymer, the organic radicals of which are hydrocarbon-based radicals selected from the group consisting of: alkyl radicals having from 1 to 20 carbon atoms; cycloalkyl radicals having from 3 to 8 carbon atoms; alkenyl radicals having from 2 to 8 carbon atoms and cycloalkenyl radicals having from 5 to 6 carbon atoms;
from 0.1 to 60 parts by weight of at least one crosslinking agent D selected from the group consisting of: polyalkoxysilanes, products originating from the partial hydrolysis of a polyalkoxysilane, and polyalkoxysiloxanes;
from 0 to 60 parts by weight of an adhesion promoter E;
from 5 to 200 parts by weight of at least one siliceous, organic and/or non-siliceous mineral filler F;
from 0.001 to 10 parts by weight of water;
from 0 to 100 parts by weight of at least one nonreactive linear polyorganosiloxane polymer G comprising a linear homopolymer or copolymer, of which, per molecule, the monovalent organic substituents, which are identical to or different from one another and which are bonded to the silicon atoms, are selected from alkyl, cycloalkyl, alkenyl, aryl, alkylarylene and arylalkylene radicals;
from 0 to 20 parts by weight of a coloring base or of a coloring agent H;
from 0 to 70 parts by weight of polyorganosiloxane resins I; and
from 0 to 20 parts of auxiliary additives J selected from among plasticizers, crosslinking retardants, mineral oils, antimicrobial agents or heat stabilizers, titanium, iron or cerium oxides;
and,
(b) from 0.1 to 50 parts by weight of the catalyst system X.

### Claim 14 (depends on 1, 11)

An elastomer obtained by crosslinking and curing of the two-component system as defined by claim 11, or of the RTV-organopolysiloxane composition as defined by claim 1.

### Claim 15

A catalyst system X comprising:
at least one metal complex or salt A of formula (1) below:
[M(L1)r1(L2)r2(Y)x] (1)
in which:
r1≧1, r2≧0 and x≧2;
the symbol M is a metal selected from the group consisting of: copper, aver, iron, boron, scandium, cerium, ytterbium, bismuth, molybdenum, germanium and manganese;
the symbol L1 is a ligand which is a β-dicarbonylato anion or the enolate anion of a β-dicarbonyl-containing compound and when r1≧2, the symbols L1 are identical or different;
the symbol L2 is an anionic ligand which is different from L1 and when r2≧2, the symbols L2 are identical or different; and
the symbol Y is a neutral ligand and when x≧2, the symbols Y are identical or different;
wherein the catalyst system X is prepared according to the following process:
step 1: the metal complex or salt A is dispersed in at least one oily organopolysiloxane polymer K, the viscosity of which is at least 100 mPa·s, and
step 2: the mixture is milled, optionally after kneading, until a homogeneous mixture is obtained, which is the catalyst system X.

### Claim 16 (depends on 15)

A process for the catalytic polycondensation reaction of organopolysiloxanes, wherein the catalyst therefor comprises the catalyst system X as defined by claim 15.

### Claim 17

A catalyst system X comprising a milled homogeneous mixture of a silicone oil having a viscosity of at least 100 mPa·s and at least one metal complex or salt A of formula (1) below:
[M(L1)r1(L2)r2(Y)x] (1)
in which:
r1≧1, r2≧0 and x≧0;
the symbol M is a metal selected from the group consisting of: copper, silver, iron, boron, scandium, cerium, ytterbium, bismuth, molybdenum, germanium and manganese;
the symbol L1 is a ligand which is a β-dicarbonylato anion or the enolate anion of a β-dicarbonyl-containing compound and when r1≧2, the symbols L1 are identical or different;
the symbol L2 is an anionic ligand which is different from L1 and when r2≧2, the symbols L2 are identical or different; and
the symbol Y is a neutral ligand and when x≧2, the symbols Y are identical or different.