Water-blown, flame retardant rigid polyurethane foam
View Patent ↗The present invention provides a flame-retardant polyurethane foam made with non chlorofluorocarbon/hydrogenated chlorofluorocarbon-containing blowing agents and without trimethylolpropane-based polyols that achieves a Class I rating as determined by a modification of the ASTM E-84 tunnel test and may find application in electronic cabinetry, architectural decorative moldings, and interior transportation vehicle walls.
1. A rigid flame retardant polyurethane foam which satisfies the requirements of ASTM E-84 for a Class I foam comprising the reaction product of:
at least one polyisocyanate; with
a polyol component comprising,
from about 2 wt. % to about 35 wt. %, based on the weight of the polyol component, of at least one sucrose-based polyol,
from about 2 wt. % to about 35 wt. %, based on the weight of the polyol component, of at least one non sucrose-based isocyanate-reactive compound, and
from about 1 wt. % to about 13 wt. %, based on the weight of the foam, of at least one aromatic polyester polyol,
in the presence of water, and optionally, at least one of carbon dioxide, surfactants, flame retardants, pigments, catalysts and fillers,
with the proviso that the rigid polyurethane foam contains no trimethylolpropane-based polyols.
2. The rigid polyurethane foam according to claim 1 , wherein the at least one polyisocyanate is chosen from ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-and-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate), 2,4- and 2,6-hexahydrotoluene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI, or HMDI), 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate (TDI), diphenylmethane-2,4′- and/or -4,4′-diisocyanate (MDI), naphthylene-1,5-diisocyanate, triphenyl-methane-4,4′,4″-diisocyanate, polyphenyl-polymethylene-polyisocyanates (crude MDI), norbornane diisocyanates, m- and p-isocyanatophenyl sulfonylisocyanates, perchlorinated aryl polyisocyanates, carbodiimide-modified polyisocyanates, urethane-modified polyisocyanates, allophanate-modified polyisocyanates, isocyanurate-modified polyisocyanates, urea-modified polyisocyanates, biuret containing polyisocyanates and isocyanate-terminated prepolymers.
3. The rigid polyurethane foam according to claim 1 , wherein the at least one polyisocyanate is an isocyanate-terminated prepolymer.
4. The rigid polyurethane foam according to claim 1 , wherein the isocyanate index is from about 100 to about 400.
5. The rigid polyurethane foam according to claim 1 , wherein the isocyanate index is from about 105 to about 200.
6. The rigid polyurethane foam according to claim 1 , wherein the at least one sucrose-based polyol comprises from about 4 wt. % to about 20 wt. %, based on the weight of the polyol component.
7. The rigid polyurethane foam according to claim 1 , wherein the at least one non sucrose-based isocyanate-reactive compound is chosen from polyethers, polyesters, polyacetals, polycarbonates, polyesterethers, polyester carbonates, polythioethers, polyamides, polyesteramides, polysiloxanes, polybutadienes and polyacetones.
8. The rigid polyurethane foam according to claim 1 , wherein the at least one non sucrose-based isocyanate-reactive compound is a polyether polyol.
9. The rigid polyurethane foam according to claim 1 , wherein the at least one non sucrose-based isocyanate-reactive compound comprises from about 4 wt. % to about 20 wt. %, based on the weight of the polyol component.
10. The rigid polyurethane foam according to claim 1 , wherein the at least one aromatic polyester polyol comprises from about 5 wt. % to about 13 wt. %, based on the weight of the foam.
11. The rigid polyurethane foam according to claim 1 , wherein the catalyst comprises one or more chosen from triethylamine, tributylamine, triethylene diamine, N-methylmorpholine, N-ethylmorpholine, N,N,N′,N′-tetramethylethylene diamine, pentamethyldiethylene triamine, 1,4-diazabicyclo[2.2.2]octane, N-methyl-N′-(dimethylaminoethyl)piperazine, bis(dimethylaminoalkyl)piperazines, N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, N,N-diethylbenzylamine, bis(N,N-diethylaminoethyl)adipate, N,N,N′,N′-tetramethyl-1,3-butanediamine, N,N-dimethyl-β-phenylethylamine, amine salt of diazabicycloundecene and formic acid, 1,2-dimethylimidazole, 2-methylimidazole, monocyclic and bicyclic amidines, bis(dialkylamino)alkyl ethers, triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine, dioctyl tin mercaptide, tin(II) acetate, tin(II) octoate, tin(II) ethylhexoate, tin(II) laurate, dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetate, dibutyltin maleate, and dioctyltin diacetate, bismuth neodecanoate, bismuth versalate, bismuth carboxylates, zinc neodecanoate, zinc versalate and carboxylic acid salts containing zinc and bismuth.
12. The rigid polyurethane foam according to claim 1 , wherein the flame retardant is chosen from phosphonates, phosphites, phosphates, halogen-containing compounds, melamine, antimony oxides, zinc compounds, aluminum compounds, magnesium compounds and mixtures thereof.
13. The rigid polyurethane foam according to claim 1 , wherein the flame retardant is chosen from dimethyl methylphosphonate, diethyl ethyl phosphonate, triethylphosphonate, ammonium polyphosphate, brominated diphenyl ethers and other brominated aromatic and aliphatic compounds, melamine, antimony pentoxide, antimony trioxide, zinc borates, alumina trihydrate, magnesium hydroxide, neutralcyclic phosphate and phosphonate esters, and mixtures thereof.
14. The rigid polyurethane foam according to claim 1 , wherein the flame retardant comprises from about 5 wt. % to about 75 wt. %, based on the weight of the polyol component.
15. The rigid polyurethane foam according to claim 1 , wherein the flame retardant comprises from about 10 wt. % to about 65 wt. %, based on the weight of the polyol component.
16. The rigid polyurethane foam according to claim 1 , wherein the flame retardant comprises from about 10 wt. % to about 55 wt. %, based on the weight of the polyol component.
17. The rigid polyurethane foam according to claim 1 , wherein the filler is chosen from glass fibers, glass flakes, cut fibers, mats, microspheres, mica, wollastonite, carbon fibers, carbon black, talc, calcium carbonate, barium sulfate, calcium silicate, clays, kieselguhr, whiting, mica, liquid crystal fibers and aramide fibers.
18. One of an electronic cabinet, an architectural decorative molding, and an interior transportation vehicle wall comprising the rigid polyurethane foam according to claim 1 .
19. A process for making a rigid flame retardant polyurethane foam which satisfies the requirements of ASTM E-84 for a Class I foam comprising reacting:
at least one polyisocyanate; with
a polyol component comprising,
from about 2 wt % to about 35 wt. %, based on the weight of the polyol component, of at least one sucrose-based polyol,
from about 2 wt. % to about 35 wt. %, based on the weight of the polyol component, of at least one non sucrose-based isocyanate-reactive compound, and
from about 1 wt. % to about 13 wt. %, based on the weight of the foam, of at least one aromatic polyester polyol,
in the presence of water, and optionally, at least one of carbon dioxide, surfactants, flame retardants, pigments, catalysts and fillers,
with the proviso that the rigid polyurethane foam contains no trimethylolpropane-based polyols.
20. The process according to claim 19 , wherein the at least one polyisocyanate is chosen from ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-and-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate), 2,4- and 2,6-hexahydrotoluene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI, or HMDI), 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate (TDI), diphenylmethane-2,4′- and/or -4,4′-diisocyanate (MDI), naphthylene-1,5-diisocyanate, triphenyl-methane-4,4′,4″-triisocyanate, polyphenyl-polymethylene-polyisocyanates (crude MDI), norbornane diisocyanates, m- and p-isocyanatophenyl sulfonylisocyanates, perchlorinated aryl polyisocyanates, carbodiimide-modified polyisocyanates, urethane-modified polyisocyanates, allophanate-modified polyisocyanates, isocyanurate-modified polyisocyanates, urea-modified polyisocyanates, biuret containing polyisocyanates and isocyanate-terminated prepolymers.
21. The process according to claim 19 , wherein the at least one polyisocyanate is an isocyanate-terminated prepolymer.
22. The process according to claim 19 , wherein the isocyanate index is from about 100 to about 400.
23. The process according to claim 19 , wherein the isocyanate index is from about 105 to about 200.
24. The process according to claim 19 , wherein the at least one sucrose-based polyol comprises from about 4 wt. % to about 20 wt. %, based on the weight of the polyol component.
25. The process according to claim 19 , wherein the at least one non sucrose-based isocyanate-reactive compound is chosen from polyethers, polyesters, polyacetals, polycarbonates, polyesterethers, polyester carbonates, polythioethers, polyamides, polyesteramides, polysiloxanes, polybutadienes and polyacetones.
26. The process according to claim 19 , wherein the at least one non sucrose-based isocyanate-reactive compound is a polyether polyol.
27. The process according to claim 19 , wherein the at least one non sucrose-based isocyanate-reactive compound comprises from about 4 wt. % to about 20 wt. %, based on the weight of the polyol component.
28. The process according to claim 19 , wherein the at least one aromatic polyester polyol comprises from about 5 wt. % to about 13 wt. %, based on the weight of the foam.
29. The process according to claim 19 , wherein the catalyst comprises one or more chosen from triethylamine, tributylamine, triethylene diamine, N-methylmorpholine, N-ethylmorpholine, N,N,N′,N′-tetramethylethylene diamine, pentamethyldiethylene triamine, 1,4-diazabicyclo[2.2.2]octane, N-methyl-N′-(dimethylaminoethyl)piperazine, bis(dimethylaminoalkyl)piperazines, N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, N,N-diethylbenzylamine, bis(N,N-diethylaminoethyl)adipate, N,N,N′,N′-tetramethyl-1,3-butanediamine, N,N-dimethyl-β-phenylethylamine, amine salt of diazabicycloundecene and formic acid, 1,2-dimethylimidazole, 2-methylimidazole, monocyclic and bicyclic amidines, bis(dialkylamino)alkyl ethers, triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine, dioctyl tin mercaptide, tin(II) acetate, tin(II) octoate, tin(II) ethylhexoate, tin(II) laurate, dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetate, dibutyltin maleate, and dioctyltin diacetate, bismuth neodecanoate, bismuth versalate, bismuth carboxylates, zinc neodecanoate, zinc versalate and carboxylic acid salts containing zinc and bismuth.
30. The process according to claim 19 , wherein the flame retardant is chosen from phosphonates, phosphites, phosphates, halogen-containing compounds, melamine, antimony oxides, zinc compounds, aluminum compounds, magnesium compounds, urea and mixtures thereof.
31. The process according to claim 19 , wherein the flame retardant is chosen from dimethyl methylphosphonate, diethyl ethyl phosphonate, triethylphosphonate, ammonium polyphosphate, brominated diphenyl ethers and other brominated aromatic and aliphatic compounds, melamine, antimony pentoxide, antimony trioxide, zinc borates, alumina trihydrate, magnesium hydroxide, neutralcyclic phosphate and phosphonate esters, urea and mixtures thereof.
32. The process according to claim 19 , wherein the flame retardant comprises from about 5 wt. % to about 75 wt. %, based on the weight of the polyol component.
33. The process according to claim 19 , wherein the flame retardant comprises from about 10 wt % to about 65 wt. %, based on the weight of the polyol component.
34. The process according to claim 19 , wherein the flame retardant comprises from about 10 wt. % to about 55 wt. %, based on the weight of the polyol component.
35. The process according to claim 19 , wherein the filler is chosen from glass fibers, glass flakes, cut fibers, mats, microspheres, mica, wollastonite, carbon fibers, carbon black, talc, calcium carbonate, barium sulfate, calcium silicate, clays, kieselguhr, whiting, mica, liquid crystal fibers and aramide fibers.
36. The foam made by the process according to claim 19 .
37. One of an electronic cabinet, an architectural decorative molding, and an interior transportation vehicle wall comprising the rigid polyurethane foam made by the process according to claim 19 .