Moisture curable organopolysiloxane compositions
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 La(III) complexes that are particularly suitable as replacements for organotin for sealant and RTV formulations. The La(III) complexes are comparable to organotin such as DBTDL 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:
(A) a polymer having at least a reactive silyl group;
(B) a crosslinker or chain extender;
(C) a catalyst chosen from a lanthanum (III) (La-III) complex;
(D) at least one adhesion promoter chosen from a silane or siloxane other than the compounds listed under (B);
(E) optionally, a filler component; and
(F) at least one co-catalyst chosen from an acidic compound.
2. The composition of claim 1 , wherein the metal catalyst component (C) comprises a La(III) complex of the formula (1):
La III Y 3-c A c (1)
wherein Y is a chelating ligand chosen from a diketonate, a diamine, a triamine, an aminoacetate, a nitriloacetate, a bipyridin, a glyoxime, or a combination of two or more thereof; and A is an anion, and c is a number between 0 to 2 or an integer.
3. The composition of claim 2 , wherein the chelating agent Y comprises a substituted or unsubstituted diketonate.
4. The composition of claim 2 , wherein the anion A is chosen from a branched C4-C19-alkyl carboxylic acid, a C4-C12-alkylsulfonate, or a combination thereof.
5. The composition of claim 1 - 4 , comprising component (C) in an amount of about 0.01 to about 7 parts per weight per 100 parts per weight of the polymer (A).
6. The composition of claim 1 , comprising component (C) in an amount of about 0.05 to about 5 parts per weight per 100 parts per weight of the polymer (A).
7. The composition of claim 1 , comprising component (C) in an amount of about 0.01 to about 1.0 parts per weight per 100 parts per weight of the polymer (A).
8. The composition of claim 1 , comprising component (C) in an amount of about 0.02 to about 0.4 parts per weight per 100 parts per weight of the polymer (A).
9. The composition of claim 1 , wherein the component (F) is chosen from a mono ester of a phosphate; a phosphonate of the formula (R 3 O)PO(OH) 2 , (R 3 O)P(OH) 2 , or R 3 P(O)(OH) 2 where R 3 is a C 1 -C 18 -alkyl, a C 2 -C 20 -alkoxyalkyl, phenyl, a C 7 -C 12 -alkylaryl, a poly(C 2 -C 4 -alkylene) oxide ester or its mixtures with diesters; a branched alkyl C 4 -C 30 -alkyl carboxylic acid; or a combination of two or more thereof.
10. The composition of claim 1 , wherein the component (F) comprises a mixture of branched alkyl C 4 -C 30 alkyl carboxylic acid comprising C 5 -C 30 acids having an alpha tertiary carbon.
11. The composition of claim 1 , comprising from about 0.01 to about 5 wt. % of the component (F).
12. The composition of claim 1 comprising the component (F) in an amount of from about 0.01 to about 8 pt. wt. per 100 pt. wt. of component (A).
13. The composition of claim 1 comprising the component (F) in an amount of from about 0.02 to about 1 pt. wt. per 100 pt. wt. of component (A).
14. 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 polypropylene; a polyesterether; and a polyorganosiloxane having units of R 3 SiO 1/2 , R 2 SiO, RSiO 3/2 , and/or SiO 4/2 ,
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, a C 1 -C 8 -alkoxy, a C 2 -C 18 -alkoxyalkyl, an oximoalkyl, an enoxyalkyl, an aminoalkyl, a carboxyalkyl, an amidoalkyl, an amidoaryl, a 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.
15. The composition of claim 1 , wherein the component (B) is chosen from an alkoxysilane, an alkoxysiloxane, an oximosilane, an oximosiloxane, an enoxysilane, an enoxysiloxane, an aminosilane, a carboxysilane, a carboxysiloxane, an alkylamidosilane, an alkylamidosiloxane, an arylamidosilane, an arylamidosiloxane, an alkoxyaminosilane, an alkaryaminosiloxane, an alkoxycarbamatosilane, an alkoxycarbamatosiloxane, and combinations of two or more thereof.
16. The composition of claim 1 wherein the crosslinker component (B) is chosen from tetraethylorthosilicate (TEOS); a polycondensate of TEOS; methyltrimethoxysilane (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(l-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.
17. The composition of claim 1 , wherein the adhesion promoter component (D) is chosen from an aminoalkyltrialkoxysilane, an aminoalkylalkyldialkoxysilane, a bis(alkyltrialkoxysilyl)amine, a tris(alkyltrialkoxysilyl)amine, a tris(alkyltrialkoxysilyl)cyanuarate, and a tris(alkyltrialkoxysilyl)isocyanuarate, or a combination of two or more thereof.
18. 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).
19. 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).
20. The composition of claim 1 , wherein the polymer component (A) is chosen from a polyorganosiloxane comprising divalent units of the formula [R 2 SiO] in the backbone, wherein R 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.
21. The polymer composition of claim 20 wherein the polymer component (A) has the formula (3):
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 (3)
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; 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 enoxyalkyl, an aminoalkyl, a carboxyalkyl, an amidoalkyl, an amidoaryl, a carbamatoalkyl, or a combination of two or more thereof, and
Z is —O—, bond, or —C 2 H 4 —.
22. The composition of claim 1 further comprising a solvent chosen from an alkylbenzene, a trialkyphosphophate, 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.
23. The composition of claim 1 , wherein the composition is provided as a one part composition.
24. The composition of claim 1 comprising:
100 pt. wt of component (A),
0.1 to about 10 pt. wt of at least one crosslinker (B),
0.01 to about 7 pt. wt. of a catalyst (C),
0.1 to about 5 pt. wt. of an adhesion promoter (D),
0 to about 300 pt. wt of component (E),
0.01 to about 8 pt. wt. of component (F),
whereby this composition can be stored in the absence of humidity and is curable in the presence of humidity upon exposure to ambient air.
25. The composition of claim 1 , wherein the composition is a two-part composition comprising:
(i) a first portion comprising the polymer component (A), optionally the filler component (E), and optionally the acidic compound (F);
(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).
26. The two-part composition of claim 25 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), 0.1 to 5 pt. wt. of an adhesion promoter (D), and 0.02 to 3 pt. wt. component (F).
27. A method of providing a cured material comprising exposing the composition of claim 1 to ambient air.
28. A method of providing a cured material comprising combining the first portion and the second portion of claim 25 and curing the mixture.
29. The method of claim 27 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.
30. A cured polymer material formed from the composition of claim 1 .
31. The cured polymer material of claim 30 in the form of an elastomeric or duromeric seal, an adhesive, a coating, an encapsulant, a shaped article, a mold, and an impression material.