Moisture curable compound with metal-arene complexes
View Patent ↗The present invention provides curable compositions comprising non-tin metal accelerators that accelerate the condensation curing of moisture-curable silicones/non-silicones. In particular, the present invention provides an accelerator comprising metal-arene complexes that are suitable as replacements for organotin in sealant and RTV formulations.
1. A composition for forming a curable polymer composition comprising:
(A) a polymer having at least a reactive silyl group;
(B) a crosslinker or chain extender; and
(C) a condensation accelerator comprising a metal-arene complex, wherein the metal-arene complex is chosen from a compound of the formula:
[(R 9 ) k (R 10 ) l M′ (m)][R 11 ] p
(R 9 ) q (R 10 ) r M″ (m) (R 11 ) s (L) t
(R 9 ) 2 M′″ (m) (R 11 ) u (L) v
or a combination of two or more thereof, wherein:
M′ is a metal atom chosen from Cr, V, Mn, Fe, Ru, Os, Co, or Ni;
M″ is a metal atom chosen from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, Mn, Fe, Ru, or Co;
M′″ is a metal atom chosen from Sc, Y, Lu, Ti, Zr, Hf, V, Nb, Cr, Mo, W, Mn, La, Ce, Sm, or Yb;
R 9 may be the same or different, substituted or unsubstituted, and is independently chosen from indenyl, tetrahydroindenyl, fluorenyl, octahydrofluorenyl, tetrahydrofluorenyl, or cyclopentadienyl, the R 9 group having a hapticity of either 3 or 5, and where a substituted R 9 group is substituted with from one to five substituents independently chosen from an alkyl, an alkenyl, an alkynyl, an aryl, an aralkyl, an amino, a heteroalkyl, a carboxy acid, a carboxy ester, an aminocarbonyl, an amino, a sulfinyl, a sulfonyl, a phosphino, a silyl, a germyl, a halo, a cyano, a hydrocarbyloxy, and combinations of two or more thereof;
R 10 may be the same or different and is independently selected from benzene and R-substituted benzene, and the substituted benzene group being substituted with from one to six substituents independently chosen from an alkyl, an aryl, an aralkyl, an amino, an alkoxy, an aryloxy, an alkylthio, an arylthio, a silyl, a germyl, a halo, a cyano, a hydrocarbyloxy, and combinations of two or more thereof;
R 11 is either a coordinated ligand, a counterion, or both, and is independently selected from a hydride, an alkyl, a cycloalkyl, a η 1 -cyclopentadienyl, a η 3 -cyclopentadienyl, a η 5 -cyclopentadienyl, a carbonyl, an acetylacetonate, an acetoacetate, a cyanide, an amide, a carboxamide, a sulfonamide, a bis(sulfonyl)amide, an azide, a nitrosyl, an oxo, a hydroxy, an alkoxide, a siloxide, an aryloxide, a carboxylate, a sulfonate, a halide, a sulfide, a mercaptan, a sulfoxide, a phosphonite, a phosphate, a phosphite, a nitrate, a sulfate, a sulfite, an arylborate, a fluoroborate, a fluorophosphate, a fluoroantimonate, a chlorate, a bromate, an iodate, an alkoxyaluminum, a hydroxoaluminate, or a cyanometallate, and may be the same or different
k+p=m, k is 0 to 2, 1 is 0 to 2, p is 0 to 1;
q+s=m, q is 0 or 1, r is 0 or 1, s is 1 to 4, t is from 0 to 5, with the proviso that q and r cannot both be 1;
u+2=m, v is 0 to 10, u is 0 to 4;
m is the oxidation state of metal atom M; and
L is a neutral ligand.
2. The composition of claim 1 , comprising the metal-arene complex of the formula [(R 9 ) k (R 10 ) l M′ (m) ][R 11 ] p .
3. The composition of claim 2 , where two R 9 groups, an R 9 and an R 10 group, an R 9 and an R 11 group, two R 10 groups, an R 10 and an R 11 group, or two R 11 groups are connected by at least one carbon- or silicon-based bridge such that they form a multidentate ligand.
4. The composition of claim 1 , comprising the metal-arene complex of the formula:
(R 9 ) q (R 10 ) r M″ (m) (R 11 ) s (L) t .
5. The composition of claim 4 , wherein combinations of an R 9 and an R 11 group, an R 9 and an L group, an R 10 and an R 11 group, an R 10 and an L group, two R 11 groups, an R 11 group and an L group, or two L groups are connected by at least one carbon- or silicon-based bridge such that they form a multidentate ligand.
6. The composition of claim 1 comprising the metal-arene complex of the formula:
(R 9 ) 2 M′″ (m) (R 11 ) u (L) v .
7. The composition of claim 6 , wherein combinations of two R 9 groups, two R 11 groups, an R 11 and an L group, or two L groups are connected by at least one carbon- or silicon-based bridge such that they form a multidentate ligand.
8. The composition of claim 1 comprising from about 0.001 to about 10 parts per weight of accelerator (C) per 100 parts per weight of the polymer (A).
9. The composition of claim 1 comprising from about 0.1 to about 5 wt. pt. of accelerator (C) per 100 parts of the polymer A.
10. The composition of claim 1 , wherein the accelerator (C) is substantially free of tin.
11. The polymer composition of claim 1 , wherein the polymer (A) has the formula (1):
[R 1 a R 2 3-a Si—Z—] n —X—Z—SiR 1 a R 2 3-a (1)
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 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.
12. The polymer composition of claim 1 wherein the polymer component (A) has the formula (2):
R 2 3-c R 1 c Si—Z—[R 2 SiO] x [R 1 2 SiO] y —Z—SiR 1 c R 2 3-c (2)
where 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 Z is a bond, a divalent unit selected from the group of a C 1 -C 8 alkylene, or O; R is C 1 -C 6 alkyl (an exemplary alkyl being methyl); x is 0 to about 10,000, in one embodiment from 11 to about 2500; and y is 0to about 10,000; preferably 0 to 500 In one embodiment, Z in a compound of formula (2) is a bond or a divalent C 1 -C 14 alkylene group, especially preferred is —C 2 H 4 —.
13. The polymer composition of claim 1 wherein the polymer component (A) has the formula (3):
R 2 3-c-d SiR 3 c R 4 d—[OSiR 3 R 4 ] x —[OSiR 3 R 4 ] y —OSiR 3 e R 4 f R 2 3-e-f (3)
where x is 0 to 10000; y is 0 to 1000; c, d, and f are independently chosen from 0 to 2; 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 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 —; and R 3 and R 4 can be identical or different on the same silicon atom and are chosen from hydrogen; C 1 -C 10 alkyl; C 1 -C 10 heteroalkyl, C 3 -C 12 cycloalkyl; C 2 -C 30 heterocycloalkyl; C 6 -C 13 aryl; C 7 -C 30 alkylaryl; C 7 -C 30 arylalkyl; C 4 -C 12 heteroaryl; C 5 -C 30 heteroarylalkyl; C 5 -C 30 heteroalkylaryl; C 2 -C 100 polyalkylene ether; or a combination of two or more thereof.
14. The composition of claim 1 , wherein the polymer (A) is chosen from silylated polyurethane (SPUR), silylated polyester, silylated polyether, silylated polycarbonate, silylated polyolefins silylated polyesterether and combinations of two or more thereof.
15. The composition of claim 14 , wherein the silylated polyolefins are chosen from polyethylene and polypropylene.
16. The composition of claim 1 , wherein the crosslinker or chain extender (B) is 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, or a combination of two or more thereof.
17. The composition of claim 1 , wherein the crosslinker or chain extender (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; methymethoxybis(ethymethylketoximo)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.
18. The composition of claim 1 comprising an adhesion promoter component (D), chosen from an (aminoalkyl)trialkoxysilane, an (aminoalkyl)alkyldialkoxysilane, a bis(trialkoxysilylalkyl)amine, a tris(trialkoxysilylalkyl)amine, a tris(trialkoxyilylalkyl)cyanurate, a tri s(trialkoxysilylalkyl)isocyanurate, an (epoxyalkyl)alkyldialkoxysilane, an (epoxyalkyl)trialkoxysilane, or a combination of two or more thereof.
19. The composition of claim 1 comprising a filler component (E).
20. The composition of claim 1 , wherein the composition is a two-part composition comprising: (i) a first portion comprising the polymer component (A), optionally a filler component (E), and optionally an acidic compound (F); and (ii) a second portion comprising the crosslinker (B), the accelerator (C), an adhesion 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).
21. A cured polymer formed from the composition of claim 1 .
22. The curable polymer of claim 21 in the form of an elastomeric seal, duromeric seal, an adhesive, a coating, an encapsulant, a shaped article, a mold, an impression material, an optical material, or a silicone foam.