Moisture curable organopolysiloxane composition
View Patent ↗The present invention provides curable compositions comprising non-Sn organo-metal catalysts that accelerate the condensation curing of moisture curable silicones/non-silicones. In particular, the present invention provides Mn(III) complexes that are particularly suitable as replacements for organotin for sealant and RTV formulations. The Mn(III) complexes are comparable or superior to organotin such as DBTDL, superior to Mn(II) compounds, and exhibit certain behavior in the presence of components that allow for tuning or adjusting the cure characteristics of the present compositions and provide good adhesion and storage stability.
1. A composition for forming a cured polymer composition comprising:
100 pt. wt of component (A) of formula
R 2 3-a R 1 a Si—Z—[R 2 SiO] x [R 1 2 SiO] y —Z—SiR 1 a R 2 3-a
whereby
x is 0 to 10000;
y is 0 to 1000;
a is 0 to 2;
R is methyl;
R 1 is chosen from a C 1 -C 10 -alkyl; a C 1 -C 10 alkyl substituted with one or more of Cl, F, N, O or S; a phenyl; or a combination of two or more thereof, and other siloxane units may be present in amounts less than 10 mol. % preferably methyl, vinyl, phenyl;
R 2 is chosen from OH, a C 1 -C 8 -alkoxy, a C 2 -C 18 -alkoxyalkyl, or a combination thereof, and
Z is —O—, bond, or —C 2 H 4 —,
0.1 to about 10 pt. wt of at least one crosslinker (B) selected from a silane, the silane having two or more reactive groups and combinations thereof,
0.01 to about 7 pt. wt. of a catalyst (C) comprises a Mn(III) complex of the formula:
Mn III Y 3
wherein Y is a chelating ligand is a diketonate,
0.1 to about 5 pt. wt. of an adhesion promoter (D) selected from an aminoalkyltrialkoxysilane, an aminoalkylalkyldialkoxysilane, a bis(alkyl-trialkoxysilyl)amine, a tris(alkyltrialkoxysilyl)amine or a combination thereof,
0 to about 300 pt. wt of component (E) a filler component,
0.01 to about 1.0 pt. wt. of component (F) branched alkyl carboxylic acid,
whereby the composition are stored in the absence of humidity and is curable in the presence of humidity upon exposure to ambient air.
2. The composition of claim 1 , wherein the component (F) is chosen from a branched alkyl C 4 -C 14 -alkyl carboxylic acids or a combination of two or more thereof.
3. The composition of claim 1 , wherein the crosslinker component (B) is chosen from tetraethylorthosilicate (TEOS), a polycondensate of TEOS; methyltrimethoxysilane (MTMS); a polycondensate of MTMS vinyl-trimethoxysilane; methylvinyldimethoxysilane; dimethyldiethoxysilane; vinyltriethoxysilane; tetra-n-propylorthosilicate; vinyltris(methylethylketoxime)silane; methyltris(methylethylketoxime)silane; trisacetamidomethylsilane; bisacetamidodimethylsilane; tris(N-methyl-acetamido)methylsilane; bis(N-methylacetamido)dimethylsilane; (N-methyl-acetamido)methyldialkoxysilane; trisbenzamidomethylsilane; trispropenoxymethylsilane; alkyldialkoxyamidosilanes; alkylalkoxybisamidosilanes; CH 3 Si(OC 2 H 5 ) 1-2 (NHCOR) 2-1 ; (CH 3 Si(OC 2 H 5 )(NCH 3 COC 6 H 5 ) 2 , CH 3 Si(OC 2 H 5 )—(NHCOC 6 H 5 ) 2 ; methyldimethoxy(ethylmethylketoximo)silane; methylmethoxybis-(ethylmethylketoximo)silane; methyldimethoxy(acetaldoximo)silane; methyldimethoxy(N-methylcarbamato)silane; ethyldimethoxy(N-methylcarbamato)silane; methyldimethoxyisopropenoxysilane; trimethoxyisopropenoxysilane; methyltri-iso-propenoxysilane; methyldimethoxy(but-2-ene-2-oxy)silane; methyldimethoxy(1-phenylethenoxy)silane; methyldimethoxy-2(1-carboethoxypropenoxy)silane; methylmethoxydi-N-methylaminosilane; vinyldimethoxymethylaminosilane; tetra-N,N-diethylaminosilane; methyldimethoxymethylaminosilane; methyltricyclohexylaminosilane; methyldimethoxyethylaminosilane; dimethyldi-N,N-dimethylaminosilane; methyldimethoxyisopropylaminosilane dimethyldi-N,N-diethylaminosilane; ethyldimethoxy(N-ethylpropionamido) silane; methyldimethoxy(N-methylacetamido)silane; methyltris(N-methylacetamido)silane; ethyldimethoxy(N-methylacetamido)silane; methyltris(N-methylbenzamido)silane; methylmethoxybis(N-methylacetamido)silane; methyldimethoxy(caprolactamo)silane; trimethoxy(N-methylacetamido)silane; methyldimethoxyethylacetimidatosilane; methyldimethoxypropylacetimidatosilane; methyldimethoxy(N,N′,N′-trimethylureido)silane; methyldimethoxy(N-allyl-N′,N′-dimethylureido)silane; methyldimethoxy(N-phenyl-N′,N′-dimethylureido)silane; methyldimethoxyisocyanatosilane; dimethoxydiisocyanatosilane; methyldimethoxythioisocyanatosilane; methylmethoxydithioisocyanatosilane, or a combination of two or more thereof.
4. The composition of claim 1 , comprising about 1 to about 10 wt. % of the crosslinker component (B) based on 100 wt. % of the polymer component (A).
5. The composition of claim 1 , wherein the crosslinker component (B) is chosen from a silane or a siloxane, the silane or siloxane having two or more reactive groups that can undergo hydrolysis and/or condensation reaction with polymer (A) or on its own in the presence of water and component (F).
6. The composition of claim 1 further comprising a solvent chosen from an alkylbenzene, a trialkylphosphate, a triarylphosphate, a phthalic acid ester, an arylsulfonic acid ester having a viscosity-density constant (VDC) of at least 0.86 that is miscible with a polyorganosiloxanes and catalyst component (C), a polyorganosiloxane devoid of reactive groups and having a viscosity of less than 2000 mPa·s at 25° C., or a combination of two or more thereof.
7. The composition of claim 1 , wherein the composition is provided as a one part composition.
8. The composition of claim 1 , wherein the composition is a two-part composition comprising:
(i) a first portion comprising the siloxane polymer component (A), optionally the filler component (E),
(ii) a second portion comprising the crosslinker (B), the catalyst component (C), the adhesive promoter (D), and the acidic compound (F)
whereby (i) and (ii) are stored separately until applied for curing by mixing of the components (i) and (ii).
9. The two-part composition of claim 8 where:
portion (i) comprises 100 pt. wt. of component (A), and 0 to 70 pt. wt. of component (E); and
portion (ii) comprises 0.1 to 10 pt. wt. of at least one crosslinker (B), 0.01 to 7 pt. wt. of a catalyst (C), 0 to 5 pt. wt. of an adhesion promoter (D), and 0.01 to about 1 pt. wt. component (F).
10. A method of providing a cured material comprising combining the first portion and the second portion of claim 8 and curing the mixture.
11. A method of providing a cured material comprising combining the first portion and the second portion of claim 9 and curing the mixture.
12. A method of providing a cured material comprising exposing the composition of claim 1 to ambient air, whereby the composition is stored in a sealed cartridge or flexible bag having outlet nozzles for extrusion and/or shaping of the uncured composition prior to cure.
13. A cured polymer material formed from the composition of claim 1 in the form of an elastomeric or duromeric seal, an adhesive, a coating, an encapsulant, a shaped article, a mold, and an impression material.