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 Fe(III) and Bi(III) complexes that are particularly suitable as replacements for organotin for sealant and RTV formulations. The Fe(III) and Bi(III) complexes are comparable or superior 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 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;
(C) about 0.01-7 parts per weight per 100 parts per weight of the polymer (A) of a catalyst selected from a Fe(III) complex of the Formula (1), a Bi(III) complex of the Formula (2), or a combination thereof:
Fe III Y 3-c A c (1)
Bi III Y 3-c A c (2)
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 chosen from substituted, unsubstituted alkyl- and aryl carboxylates, and c is a number between 0 to 3 or an integer;
(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 acidic compound chosen from a phosphate ester, a phosphonate, a phosphite, a phosphine, a sulfite, a pseudohalogenide, a branched alkyl carboxylic acid, and a combination of two or more thereof.
2. The composition of claim 1 , wherein the chelating agent Y comprises a substituted diketonate, the carboxylate anion A is chosen from pentanoate, hexanoate, heptanoate, octoate, neodecanoate, 2-ethylhexanoate, or a combination of two or more thereof.
3. The composition of claim 1 , wherein catalyst (C) comprises a complex Fe III Y 3-c A c whereby c=0 and Y is 3-methyl-2,4-pentadionate.
4. The composition of claim 1 , wherein catalyst (C) comprises a complex Bi III Y 3-c A c and whereby c=3 and the anion A is a branched C 4 -C 19 alkyl carboxylate.
5. The composition of claim 1 comprising the catalyst (C) in an amount of about 0.1 to about 2 parts per weight per 100 parts per weight of the polymer (A).
6. The composition of claim 1 comprising the catalyst (C) in an amount of about 0.2 to about 0.7 parts per weight per 100 parts per weight of the polymer (A).
7. The composition of claim 1 , wherein the acidic component (F) is added in a molar ratio of (F):(C) of 1:10 to 1:4.
8. 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 14 -alkyl carboxylic acid; or a combination of two or more thereof.
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 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
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), 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(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.
11. 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.
12. The composition of claim 1 comprising about 0.1 to about 5 pt. wt. of the adhesion promoter (D) per 100 parts per weight of the polymer (A).
13. 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.
14. The composition of claim 1 wherein the adhesion promoter comprises an aminoalkyltrialkoxysilane and a bis(alkyltrialkoxysilyl)amine.
15. The composition of claim 1 , wherein the adhesion promoter comprises bis(3-propyltrimethoxysilyl)amine and 3-aminopropyltrimethoxy silane.
16. 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)
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. % preferably methyl, vinyl, phenyl;
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 —.
17. The composition of claim 1 , further comprising a solvent chosen from an alkylbenzene, a trialkyphosphate, 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.
18. 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.
19. The composition of any claim 1 comprising:
100 pt. wt of component (A),
0.5 to about 3 pt. wt of at least one alkoxysilane as crosslinker (B),
0.1 to about 2 pt. wt. of Fe-III-3-methyl-penta-2,4-dionate as catalyst (C),
0.1 to about 1.5 pt. wt. of bis(3-propyltrimethoxysilyl)amine as adhesion promoter (D),
0 to about 300 pt. wt of component (E),
0.01 to about 0.5 pt. wt. of Versatic Acid™ 10 as 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.
20. The composition of claim 1 comprising:
100 pt. wt of component (A),
0.5 to about 3 pt. wt of at least one alkoxysilane as crosslinker (B),
0.1 to about 2 pt. wt. of Bi-III-(octoate) as catalyst (C),
0.1 to about 1.5 pt. wt. of Bis(3-propyltrimethoxysilyl)amine as adhesion promoter (D),
0 to about 300 pt. wt of component (E),
0.01 to about 0.5 pt. wt. of Versatic Acid™ 10 as 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.
21. The composition of claim 1 wherein the adhesion promoter comprises an aminoalkyltrialkoxysilane and a bis(alkyltrialkoxysilyl)amine.
22. The composition of claim 21 comprising about 0.1 to about 5 pt. wt. of the adhesion promoter (D) per 100 parts per weight of the polymer (A).
23. The composition of any claim 21 comprising about 0.14 to about 2 pt. wt. of the adhesion promoter (D) per 100 parts per weight of the polymer (A).
24. The composition of claim 1 , wherein the adhesion promoter comprises bis(3-propyltrimethoxysilyl)amine and 3-aminopropyltrimethoxy silane.
25. The composition of claim 24 comprising about 0.1 to about 5 pt. wt. of the adhesion promoter (D) per 100 parts per weight of the polymer (A).
26. The composition of any claim 24 comprising about 0.14 to about 2 pt. wt. of the adhesion promoter (D) per 100 parts per weight of the polymer (A).
27. A cured polymer formed from the composition of claim 1 .
28. The cured polymer of claim 27 in the form of an elastomeric, seal, duromeric seal, an adhesive, a coating, an encapsulant, a shaped article, a mold, or an impression material.