Trimerization catalysts from sterically hindered salts
View Patent ↗The present invention provides trimerization catalyst compositions having a sterically hindered carboxylate salt and methods to produce a polyisocyanurate/-polyurethane foam using such trimerization catalyst compositions.
1. A method for preparing a polyisocyanurate/polyurethane foam which comprises contacting at least one polyisocyanate comprising at least one of toluene diisocyanate and diphenyl methane diisocyanate isomers, with at least one polyol at an Isocyanate Index of 150-650, in the presence of at least one blowing agent and an effective amount of a catalyst composition comprising a solution of at least one member selected from the group consisting of potassium pivalate, potassium triethylacetate and potassium neoheptanoate;
with the proviso that the at least one blowing agent is not a chlorofluorocarbon.
2. The method of claim 1 , wherein the catalyst composition is present in an amount from about 0.05 to about 10 parts by weight per hundred weight parts of the at least one polyol.
3. The method of claim 1 further comprising
(a) forming a premix comprising:
i) at least one polyol;
ii) about 10 to about 80 parts by weight per hundred weight parts of the polyol (pphp) blowing agent;
iii) about 0.5 to about 10 pphp silicone surfactant;
iv) zero to about 10 pphp water;
v) zero to about 50 pphp flame retardant;
vi) zero to about 10 pphp urethane catalyst; and
vii) about 0.05 to about 10 pphp of the catalyst composition a; and
(b) contacting the premix with the polyisocyanate, the relative amounts of the components affording a foam having a density of 20-250 Kg/m 3 and wherein the foam has a substantially constant height rise versus time.
4. The method of claim 1 , wherein the catalyst composition comprises potassium triethylacetate, potassium neoheptanoate, or any combination thereof.
5. The method of claim 1 , wherein the catalyst composition comprises potassium pivalate.
6. The method of claim 1 , wherein the at least one blowing agent comprises water, methylene chloride, acetone, a hydrocarbon, or any combination thereof.
7. The method of claim 6 , wherein the at least one blowing agent comprises at least one hydrocarbon selected from the group consisting of n-pentane, iso-pentane, cyclopentane, or any combination thereof.
8. The method of claim 1 , wherein the at least one polyol comprises at least one polyether polyol, at least one polyester polyol, or any combination thereof.
9. The method of claim 1 , further comprising at least one alkali metal α,β-unsaturated carboxylate salt, at least one alkali metal carboxylate salt, at least one alkaline earth metal α,β-unsaturated carboxylate salt, at least one alkaline earth metal carboxylate salt, at least one quaternary ammonium α,β-unsaturated carboxylate salt, or at least one quaternary ammonium carboxylate salt, or any combination thereof.
10. The method of claim 1 , wherein the catalyst composition is thermally stable at a temperature up to about 150° C.
11. The method of claim 1 , wherein the catalyst composition is thermally stable at a temperature up to about 250° C.
12. The method of claim 1 , wherein the catalyst composition further comprises a diluent.
13. The method of claim 12 , wherein the diluents comprises ethylene glycol.
14. The method of claim 1 wherein the relative amounts of the components produce a foam having a density of 20-250 Kg/m 3 .
15. The method of claim 6 wherein the blowing agent comprises water.
16. The method of claim 1 further comprising at least one member selected from the group consisting of surfactants, flame retardants, and urethane catalysts.
17. The method of claim 16 wherein said member comprises a urethane catalyst comprising at least one member selected from the group consisting of triethylenediamine, N-methylimidazole, 1,2-dimethyl-imidazole, N-methylmorpholine, N-ethylmorpholine, triethylamine, N,N′-dimethylpiperazine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, 2,4,6-tris(dimethylaminomethyl)phenol, N-methyldicyclohexylamine, pentamethyldipropylene triamine, N-methyl-N′-(2-dimethylamino)-ethyl-piperazine, tributylamine, pentamethyl-diethylenetriamine, hexamethyl-triethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexyl-amine, pentamethyldipropylene-triamine, triethanolamine, dimethylethanolamine, bis(dimethylaminoethyl)ether, tris(3-dimethylamino)-propylamine, and 1,8-diazabicyclo[5.4.0]undecene or its acid blocked derivatives.
18. The method of claim 17 wherein said member comprises pentamethyl-diethylenetriamine.
19. The method of claim 1 further comprising at least one member selected from the group consisting of cell stabilizers, chain extenders, epoxy resins, acrylic resins, fillers and pigments.
20. The method of claim 16 wherein the flame retardant comprises trichloropropylphosphate.
21. The method of claim 7 wherein the blowing agent comprises n-pentane.
22. A method for preparing a polvisocvanurate/polvurethane foam which comprises contacting at least one polvisocvanate comprising at least one of toluene diisocyanate and diphenyl methane diisocyanate isomers, with at least one polyol at an Isocyanate Index of 150-650, in the presence of at least one blowing agent and an effective amount of a catalyst composition comprising a solution of at least one sterically hindered carboxylate salt having the formula:
wherein:
R 1 R 2 and R 3 are selected independently from a C l -C 18 alkyl, alkenyl, aryl, or aralkyl, any of which are substituted or unsubstituted;
n is an integer from 0 to 10, inclusive; and
M is potassium, with the proviso that the at least one blowing agent is not a chlorofluorocarbon; and wherein said catalyst composition further comprises at least one member selected from the group consisting of tetramethylammonium pivalate, 2-hydroxyl-propyltrimethylammonium pivalate, 2-hydroxylpropyltriethylammonium pivalate, tetraethylammonium pivalate, tetrapropylammonium pivalate, tetrabutylammonium pivalate, dimethyldiallylammonium pivalate, tetramethyl-ammonium triethylacetate, 2-hydroxylpropyltrimethylammonium triethylacetate, 2-hydroxylpropyltriethylammonium triethylacetate, tetraethylammonium triethylacetate, tetrapropylammonium triethylacetate, tetrabutylammonium triethylacetate, tetramethylammonium neoheptanoate, 2-hydroxylpropyltrimethyl-ammonium neoheptanoate, 2-hydroxylpropyltriethylammonium neoheptanoate, tetraethylammonium neoheptanoate, tetrapropylammonium neoheptanoate, tetrabutyl-ammonium neoheptanoate, tetramethylammonium neooctanoate, 2-hydroxylpropyltrimethylammonium neooctanoate, 2-hydroxylpropyl-triethylammonium neooctanoate, tetraethylammonium neooctanoate, tetrapropyl-ammonium neooctanoate, tetrabutylammonium neooctanoate, tetramethylammonium neodecanoate, 2-hydroxylpropyltrimethylammonium neodecanoate, 2-hydroxylpropyltriethylammonium neodecanoate, tetraethylammonium neodecanoate, tetrapropylammonium neodecanoate, tetrabutylammonium neodecanoate, or any combination thereof.
23. The method of claim 22 , wherein R 1 , R 2 , and R 3 are selected independently from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, tolyl, and benzyl.
24. The method of claim 22 , wherein R 1 , R 2 , and R 3 are selected independently from methyl, ethyl, propyl, and butyl.
25. The method of claim 22 , wherein the integer n can range from 0 to 5, inclusive.
26. The method of claim 22 , wherein the at least one sterically hindered carboxylate salt comprises a salt of pivalic acid, triethylacetic acid, neohexanoic acid, neoheptanoic acid, neooctanoic acid, neodecanoic acid, neoundecanoic acid, neododecanoic acid, or any combination thereof.
27. The method of claim 22 wherein the member comprises tetramethylammonium pivalate.