Moisture curable composition with amino acids
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 amino acid compounds 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 an amino acid compound, chosen from a compound of the formula (6):
wherein Q is selected from
an aliphatic heterocyclic compound containing at least one nitrogen atom of the formula:
where t is an integer from 1 to 6;
or an aromatic heterocyclic compound containing at least one nitrogen atom;
where R 9 , R 10 , and R 11 are independently selected from hydrogen, a linear or branched alkyl, a linear or branched heteroalkyl, an aryl, a heteroaryl, a cycloalkyl, a heterocycloalkyl, a linear or branched aralkyl, or a linear or branched heteroaralkyl, a silyl group, as siloxy group, or a combination of two or more thereof;
R 12 is an acetyl; and
R 13 are independently selected from hydrogen, a linear or branched alkyl, a cycloalkyl, an aryl, a heteroaryl, a linear or branched aralkyl, a linear or branched heteroaralkyl, a silyl group, a siloxy group, a functional group of the formula,
or a functional group of the formula
where X is either O or S; and R 14 and R 15 are independently selected from hydrogen, a linear or branched alkyl, a cycloalkyl, an aryl, a heteroaryl, a linear or branched aralkyl, a linear or branched heteroaralkyl, OR 16 , NR 2 16 , or SR 16 ; and R 16 is chosen from hydrogen, a linear or branched alkyl, a cycloalkyl, an aryl, a heteroaryl, a linear or branched aralkyl, a linear or branched heteroaralkyl, an acyl group, a thioacyl group, or a combination of two or more thereof, and R 16 groups may be similar or different.
2. The composition of claim 1 , wherein R 9 is a group other than hydrogen.
3. The composition of claim 1 , wherein R 13 is chosen from a functional group of the formula:
4. The composition of claim 3 , wherein X is O, and R 14 is a C 1 -C 6 alkyl group.
5. The composition of claim 1 , wherein the amino acid comprises a compound of the formula:
6. The composition of claim 1 , wherein the amino acid is chosen from N-acetyl-glycine, N-acetyl-alanine, N-acetyl-valine, N-acetyl-leucine, N-acetyl-isoleucine, N-acetyl-serine, N-acetyl-threonine, N-acetyl-cysteine, N-acetyl-methionine, N-acetyl-aspartic acid, N-acetyl-asparagine, N-acetyl-glutamic acid, N-acetyl-glutamine, N-acetyl-arginine, N-acetyl-lysine, N-acetyl-histidine, N-acetyl-phenylalanine, N-acetyl-tyrosine, N-acetyl-tryptophan, N-acetyl-proline, N-acetyl-taurine, N-acetyl-hydroxyproline, N-acetyl-canavanine, N-acetyl-hydroxylysine, N-acetyl-cycloserine, N-acetyl-homoarginine, N-acetyl-norleucine, N-acetyl-norvaline, N-acetyl-homoserine, N-acetyl-methylserine, N-acetyl-hydroxyvaline, N-acetyl-ethionine, N-acetyl-methoxinine, N-acetyl-β-aminoisobutanoic acid, N-acetyl-homocysteine, N-acetyl-cysteine sulfinic acid, N-acetyl-homophenylalanine, N-acetyl-homotryptophan, N-acetyl-hydroxytryptamine (N-acetylserotonin), N-acetyl-tryptamine, N-acetyl-ornithine, N-acetyl-citrulline, N-acetyl-argininosuccinic acid, N-acetyl-dopa, N-acetyl-3-iodotyrosine, N-acetyl-3,5-diiodotyrosine, N-acetyl-3,5,3′-triiodothyronine, N-acetyl-thyroxine, N-acetyl-creatine, N-acetyl-creatinine, N-acetyl-cystine and N-acetyl-homocystine, or a combination of two or more thereof.
7. The composition of claim 1 , wherein the amino acid compound is chosen from N-acetyl-glycine trimethylsilyl ester, N-(trifluoroacetyl)-1-leucine trimethylsilyl ester, or a combination of two or more thereof.
8. The composition of claim 1 , wherein the amino acid compound comprises N-acetyl-proline.
9. 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).
10. 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.
11. The composition of claim 1 , wherein the accelerator (C) is substantially free of tin.
12. The composition of claim 1 , wherein the accelerator (C) further comprises a blend of metal accelerator, a salt of a metal accelerator, a carboxylic acid, an alkyl-sulfonic acid, an aryl sulfonic acid, an inorganic acid, an amine, a guanidine, an amidine, an inorganic base, or a combination of two or more thereof.
13. 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′ 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.
14. 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.
15. 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′ 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 aminoacyl, 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.
16. The composition of claim 1 , wherein the polymer (A) is chosen from silylated polyurethane (SPUR), silylated polyester, silylated polyether, silylated polycarbonate, silylated polyolefins like polyethylene, polypropylene, silylated polyesterether and combinations of two or more thereof.
17. 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.
18. 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; 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(l-phenylethenoxy)silane, methyldimethoxy-2-(1-carboethoxypropenoxy)silane; methyl methoxydi (N-methylamino)silane; vinyldimethoxy(methyl amino) 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; methyl di methoxy(propylacetimidato)silane; methyldimethoxy(N,N′,N′-trimethylureido)silane, methyl dimethoxy(N-allyl-N′,N′-dimethylureido)silane; methyl dimethoxy(N-phenyl-N′,N′-dimethylureido)silane; methyldimethoxyisocyanatosilane; dimethoxydiisocyanatosilane; methyldimethoxyisothiocyanatosilane; methylmethoxydiisothiocyanatosilane, the condensates thereof, or a combination of two or more thereof.
19. 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(trialkoxysilylalkyl)cyanurate, a tris(trialkoxysilylalkyl)isocyanurate, an (epoxyalkyl)alkyldialkoxysilane, an (epoxyalkyl)trialkoxysilane, or a combination of two or more thereof.
20. The composition of claim 1 comprising a filler component (E).
21. The composition of claim 1 comprising at least one acidic compound (F) chosen from a phosphate ester, a phosphonate ester, a phosphonic acid, a phosphorous acid, a phosphite, a phosphonite ester, a sulfate, a sulfite, a pseudohalogenide, a branched C 4 -C 25 alkyl carboxylic acid, or a combination of two or more thereof.
22. 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).
23. A cured polymer formed from the composition or method of claim 1 .
24. The cured polymer of claim 23 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.
25. A cured polymer composition comprising:
a compound having at least one hydridosilyl group, and
a condensation cure accelerator comprising an amino acid based compound, chosen from a compound of the formula (6):
wherein Q is selected from
an aliphatic heterocyclic compound containing at least one nitrogen atom of the formula:
where t is an integer from 1 to 6,
or an aromatic heterocyclic compound containing at least one nitrogen atom;
where R 9 , R 10 , and R 11 are independently selected from hydrogen, a linear or branched alkyl, a linear or branched heteroalkyl, an aryl, a heteroaryl, a cycloalkyl, a heterocycloalkyl, a linear or branched aralkyl, or a linear or branched heteroaralkyl, a silyl group, as siloxy group, or a combination of two or more thereof;
R 12 is an acetyl; and
R 13 are independently selected from hydrogen, a linear or branched alkyl, a cycloalkyl, an aryl, a heteroaryl, a linear or branched aralkyl, a linear or branched heteroaralkyl, a silyl group, a siloxy group, a functional group of the formula,
or a functional group of the formula
where X is either O or S; and R 14 and R 15 are independently selected from hydrogen, a linear or branched alkyl, a cycloalkyl, an aryl, a heteroaryl, a linear or branched aralkyl, a linear or branched heteroaralkyl, OR 16 , NR 2 16 , or SR 16 ; and R 16 is chosen from hydrogen, a linear or branched alkyl, a cycloalkyl, an aryl, a heteroaryl, a linear or branched aralkyl, a linear or branched heteroaralkyl, an acyl group, a thioacyl group, or a combination of two or more thereof, and R 16 groups may be similar or different.
26. The composition of claim 25 , wherein R 9 is a group other than hydrogen.
27. The composition of claim 25 , wherein the amino acid based comprises a compound of the formula:
28. The composition of claim 25 , wherein the amino acid based is chosen from N-acetyl-glycine, N-acetyl-alanine, N-acetyl-valine, N-acetyl-leucine, N-acetyl-isoleucine, N-acetyl-serine, N-acetyl-threonine, N-acetyl-cysteine, N-acetyl-methionine, N-acetyl-aspartic acid, N-acetyl-asparagine, N-acetyl-glutamic acid, N-acetyl-glutamine, N-acetyl-arginine, N-acetyl-lysine, N-acetyl-histidine, N-acetyl-phenylalanine, N-acetyl-tyrosine, N-acetyl-tryptophan, N-acetyl-proline, N-acetyl-taurine, N-acetyl-hydroxyproline, N-acetyl-canavanine, N-acetyl-hydroxylysine, N-acetyl-cycloserine, N-acetyl-homoarginine, N-acetyl-norleucine, N-acetyl-norvaline, N-acetyl-homoserine, N-acetyl-methylserine, N-acetyl-hydroxyvaline, N-acetyl-ethionine, N-acetyl-methoxinine, N-acetyl-β-aminoisobutanoic acid, N-acetyl-homocysteine, N-acetyl-cysteine sulfinic acid, N-acetyl-homophenylalanine, N-acetyl-homotryptophan, N-acetyl-hydroxytryptamine (N-acetylserotonin), N-acetyl-tryptamine, N-acetyl-ornithine, N-acetyl-citrulline, N-acetyl-argininosuccinic acid, N-acetyl-dopa, N-acetyl-3-iodotyrosine, N-acetyl-3,5-diiodotyrosine, N-acetyl-3,5,3′-triiodothyronine, N-acetyl-thyroxine, N-acetyl-creatine, N-acetyl-creatinine, N-acetyl-cystine and N-acetyl-homocystine, or a combination of two or more thereof.
29. The composition of claim 25 , wherein the amino acid based compound is chosen from N-acetyl-glycine trimethylsilyl ester, N-(trifluoroacetyl)-1-leucine trimethylsilyl ester, or a combination of two or more thereof.
30. The composition of claim 25 , wherein the amino acid based compound comprises N-acetyl-proline.
31. The composition of claim 25 comprising from about 0.001 to about 10 parts per weight of accelerator per 100 parts per weight of the compound having at least one hydrosilyl group.
32. The composition of claim 25 comprising from about 0.1 to about 5 wt. pt. of accelerator per 100 parts of the having at least one hydrosilyl group.
33. The composition of claim 25 , wherein the accelerator is substantially free of tin.
34. The composition of claim 25 , wherein the accelerator (C) further comprises a blend of metal accelerator, a salt of a metal accelerator, a carboxylic acid, an alkyl-sulfonic acid, an aryl sulfonic acid, an inorganic acid, an amine, a guanidine, an amidine, an inorganic base, or a combination of two or more thereof.