Moisture curable organopolysiloxane composition
The present invention provides curable compositions comprising non-tin metal catalysts that accelerate the condensation curing of moisture-curable silicones/non-silicones. In particular, the present invention provides bismuth(III) sulfonate complexes that are particularly suitable as replacements for organotin in sealant and RTV formulations. In one embodiment, the present invention provides bismuth (III) camphorsulfonate and bismuth(III) methanesulfonate complexes. Further, these bismuth(III) sulfonate complexes are comparable or superior to organotin such as DBTDL, 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:
(A) a polymer having at least a reactive silyl group;
(B) a crosslinker or chain extender chosen from an alkoxysilane, an alkoxysiloxane, an oximosilane, an oximosiloxane, an enoxysilane, an enoxysiloxane, an aminosilane, an aminosiloxane, a carboxysilane, a carboxysiloxane, an alkylamidosilane, an alkylamidosiloxane, an arylamidosilane, an arylamidosiloxane, an alkoxyaminosilane, an alklarylaminosiloxane, an alkoxycarbamatosilane, an alkoxycarbamatosiloxane, and combinations of two or more thereof; and
(C) a condensation catalyst comprising a bismuth(III) sulfonate complex of the formula (1):
Bi(O 3 SR 9 ) r (Q) 3-r (1)
where R 9 is chosen from a linear alkyl, a branched alkyl, a cycloalkyl, a heteroaryl, an aralkyl, a branched aralkyl, a heteroalkyl, a heterocycloalkyl, a heteroaralkyl, an aryl, or a combination of two or more thereof, Q is an anionic ligand, and r is 1 to 3, with the proviso that heteroalkyl is other than a perhaloalkyl.
2. The composition of claim 1 , wherein at least one (O 3 SR 9 ) group comprises a R 9 chosen from methyl or (7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methyl.
3. The composition of claims 1 , wherein r is 3.
4. The composition of claim 1 , wherein r is 3 and R 9 is methyl.
5. The composition of claim 1 , wherein r is 3 and R 9 is (7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methyl.
6. The composition of claim 1 , comprising from about 0.001 to about 7 parts per weight of catalyst component (C) per 100 parts per weight of the polymer (A).
7. The composition of claim 1 comprising from about 0.01 to about 7 parts per weight catalyst (C) per 100 parts per weight of the polymer (A).
8. The composition of claim 1 comprising from about 0.005 to about 0.05 wt. pt. of catalyst component (C) per 100 parts of component.
9. The polymer composition of claim 1 , wherein the polymer (A) has the formula (2):
[R 1 a R 2 3-a Si—Z—] n —X—Z—SiR 1 a R 2 3-a (2)
where X is chosen from a polyurethane; a polyester; a polyether; a polycarbonate; a polyolefin; a polyesterether; and a polyorganosiloxane having units of R 3 SiO 1/2 , R 2 SiO, RSiO 3/2 , and/or SiO 2 ;
n is 0 to 100; a is 0 to 2; R and R 1 can be identical or different at the same Si-atom and 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; a C 7 -C 16 alkylaryl; a C 7 -C 16 arylalkyl; a C 2 -C 4 polyalkylene ether; or a combination of two or more thereof; R 2 is chosen from OH, C 1 -C 8 alkoxy, C 2 -C 18 alkoxyalkyl, oximoalkyl, enoxyalkyl, aminoalkyl, carboxyalkyl, amidoalkyl, amidoaryl, carbamatoalkyl, or a combination of two or more thereof; and Z is a bond, a divalent unit selected from the group of a C 1 -C 8 alkylene, or O.
10. The composition of claim 1 , wherein the crosslinker component (B) is chosen from tetraethylorthosilicate (TEOS); methyltrimethoxysilane (MTMS); methyltriethoxysilane; vinyltrimethoxysilane; vinyltriethoxysilane; methylphenyldimethoxysilane; 3,3,3-trifluoropropyltrimethoxysilane; methyltriacetoxysilane; vinyltriacetoxysilane; ethyltriacetoxysilane; di-butoxydiacetoxysilane; phenyltripropionoxysilane; methyltris(methylethylketoximo)silane; vinyltris(methylethylketoximo)silane; 3,3,3-trifluoropropyltris(methylethylketoximo)silane; methyltris(isopropenoxy)silane; vinyltris(isopropenoxy)silane; ethylpolysilicate; dimethyltetraacetoxydisiloxane; tetra-n-propylorthosilicate; methyldimethoxy(ethylmethylketoximo)silane; methylmethoxybis(ethylmethylketoximo)silane; methyldimethoxy(acetaldoximo)silane; methyldimethoxy(N-methylcarbamato)silane; ethyldimethoxy(N-methylcarbamato)silane; methyldimethoxyisopropenoxysilane; trimethoxyisopropenoxysilane; methyltriisopropenoxysilane; methyldimethoxy(but-2-en-2-oxy)silane; methyldimethoxy(1-phenylethenoxy)silane; methyldimethoxy-2-(1-carboethoxypropenoxy)silane; methylmethoxydi(N-methylamino)silane; vinyldimethoxy(methylamino)silane; tetra-N,N-diethylaminosilane; methyldimethoxy(methylamino)silane; methyltri(cyclohexylamino)silane; methyldimethoxy(ethylamino)silane; dimethyldi(N,N-dimethylamino)silane; methyldimethoxy(isopropylamino)silane; dimethyldi(N,N-diethylamino)silane; 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; methyldimethoxy(ethylacetimidato)silane; methyldimethoxy(propylacetimidato)silane; methyldimethoxy(N,N′,N′-trimethylureido)silane; methyldimethoxy(N-allyl-N′,N′-dimethylureido)silane; methyldimethoxy(N-phenyl-N′,N′-dimethylureido)silane; methyldimethoxyisocyanatosilane; dimethoxydiisocyanatosilane; methyldimethoxyisothiocyanatosilane; methylmethoxydiisothiocyanatosilane, the condensates thereof, or a combination of two or more thereof.
11. The composition of claim 1 , further comprising an adhesion promoter component (D) is chosen from an (aminoalkyl)trialkoxysilane, an (aminoalkyl)alkyldialkoxysilane, a bis(trialkoxysilylalkyl)amine, a tris(trialkoxysilylalkyl)amine, a tris(trialkoxysilylalkyl)cyanurate, a tris(trialkoxysilylalkyl)isocyanurate, an (epoxyalkyl)alkyldialkoxysilane, an (epoxyalkyl)trialkoxysilane, or a combination of two or more thereof.
12. The polymer composition of claim 1 wherein the polymer component (A) has the formula (4):
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 (4)
where 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; a C 7 -C 16 alkylaryl; a C 7 -C 16 arylalkyl; a C 2 -C 4 polyalkylene ether; or a combination of two or more thereof, and other siloxane units may be present in amounts less than 10 mol.%; R 2 is chosen from OH, a C 1 -C 8 alkoxy, a C 2 -C 18 alkoxyalkyl, an oximoalkyl, an oximoaryl, an enoxyalkyl, an enoxyaryl, an aminoalkyl, an aminoaryl, a carboxyalkyl, a carboxyaryl, an amidoalkyl, an amidoaryl, a carbamatoalkyl, a carbamatoaryl, or a combination of two or more thereof; and Z is —O—, a bond, or —C 2 H 4 —.
13. The composition of claim 1 , wherein the catalyst system (C) is substantially free of tin and substantially free of fluorine.
14. The composition of claim 13 , wherein the catalyst system comprises 10 wt. % or less of fluorine.
15. The composition of claim 13 , wherein the catalyst system comprises 5 wt. % or less of fluorine.
16. The composition of claim 13 , wherein the catalyst system comprises 1 wt. % or less of fluorine.
17. The composition of claim 13 , wherein the catalyst system comprises 0.1 wt. % or less of fluorine.
18. The composition of claim 1 , wherein catalyst (C) comprises a blend of metal catalyst complexes.
19. A cured polymer formed from the composition or method of claim 1 .
20. The cured polymer of claim 19 in the form of an elastomeric seal, duromeric seal, an adhesive, a coating, an encapsulant, a shaped article, a mold, or an impression material.
21. A composition for forming a cured polymer composition comprising:
(A) a polymer having at least a reactive silyl group, where the polymer is free of siloxane bonds;
(B) a crosslinker or chain extender chosen from an alkoxysilane, an alkoxysiloxane, an oximosilane, an oximosiloxane, an enoxysilane, an enoxysiloxane, an aminosilane, an aminosiloxane, a carboxysilane, a carboxysiloxane, an alkylamidosilane, an alkylamidosiloxane, an arylamidosilane, an arylamidosiloxane, an alkoxyaminosilane, an alklarylaminosiloxane, an alkoxycarbamatosilane, an alkoxycarbamatosiloxane, the condensates thereof, and combinations of two or more thereof; and
(C) a condensation catalyst comprising a bismuth(III) sulfonate, with the proviso that the bismuth sulfonate does not comprise a perhaloalkyl group.
22. The composition of claim 21 , comprising a bismuth(III) sulfonate complex of the formula (1):
Bi(O 3 SR 9 ) r (Q) 3-r (1)
where R 9 is chosen from a linear alkyl, a branched alkyl, a cycloalkyl, a heteroaryl, an aralkyl, a branched aralkyl, a heteroalkyl, a heterocycloalkyl, a heteroaralkyl, an aryl, or a combination of two or more thereof, Q is an anionic ligand, and r is 1 to 3.
23. The composition of claim 21 comprising from about 0.001 to about 7 parts per weight of catalyst component (C) per 100 parts per weight of the polymer (A).
24. The composition of claim 21 comprising from about 0.01 to about 7 parts per weight catalyst (C) per 100 parts per weight of the polymer (A).
25. The composition of claim 21 comprising from about 0.005 to about 0.05 wt. pt. of catalyst component (C) per 100 parts of component.
26. The composition of claim 21 , wherein the polymer (A) is chosen from a silylated polyurethane (SPUR), a silylated polyester, a silylated polyether, a silylated polycarbonate, a silylated polyolefin, a silylated polyesterether, or a combination of two or more thereof.
27. The composition of claim 22 , wherein R 9 is chosen from an alkyl, an aryl, an aralkyl, a cycloalkyl, or a combination of two or more thereof; and Q is chosen from an alkyl, an aryl, an aralkyl, a cycloalkyl, or a combination of two or more thereof.
28. The composition of claim 22 , wherein R 9 is chosen from an alkyl, a cycloalkyl, an aryl, an aralkyl, or a combination thereof, and Q is a hydroxyl.
29. The composition of claim 22 , wherein R 9 is chosen from an alkyl, a cycloalkyl, an aryl, an aralkyl, or a combination of two or more thereof.
30. The composition of claim 22 , wherein at least one (O 3 SR 9 ) group comprises a R 9 chosen from a spirocyclic compound, a fused cyclic compound, a bridged cyclic compound, or combination of two or more thereof.
31. The composition of claim 22 , wherein at least one (O 3 SR 9 ) group comprises a R 9 chosen from methyl or (7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methyl.
32. A cured polymer formed from the composition or method of claim 21 .
33. The cured polymer of claim 32 in the form of an elastomeric seal, duromeric seal, an adhesive, a coating, an encapsulant, a shaped article, a mold, or an impression material.