Flexible polyurethane foams made from alkoxylated natural oil
View Patent ↗The present invention provides flexible conventional polyurethane foams made from at least one polyisocyanate and at least one vegetable oil alkoxylated in the presence of a double metal cyanide (DMC) catalyst, optionally at least one non-vegetable oil-based polyol, generally in the presence of a blowing agent and optionally in the presence of a surfactant, pigment, flame retardant, catalyst or filler. The alkoxylated natural oil must have (a) an ethylene oxide content in the alkoxylated segment greater than 20% by weight, (b) a primary hydroxyl group content of at least 10%, with the sum of (a)+(b) being at least 30% but no greater than 60%, The alkoxylated natural oils are environmentally-friendly, bio-based polyols which can be used to increase the “green” content of polyurethane foams without having detrimental effects on foam properties.
1. A flexible conventional polyurethane foam comprising the reaction product of:
at least one polyisocyanate; and
at least one natural oil alkoxylated in the presence of a double metal cyanide (DMC) catalyst having
(a) an ethylene oxide content in the alkoxylated segment greater than 20% by weight,
(b) a primary hydroxyl group content of at least 10%, with the sum of (a)+(b) being at least 30% but no greater than 60%,
optionally at least one petroleum-based polyol,
in the presence of at least one of blowing agent,
and optionally in the presence of one or more surfactants, pigments, flame retardants, catalysts and fillers.
2. The flexible conventional polyurethane foam of claim 1 in which 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, isocyanate-terminated prepolymers and mixtures thereof.
3. The flexible conventional polyurethane foam of claim 1 in which the at least one polyisocyanate is toluene diisocyanate (TDI).
4. The flexible conventional polyurethane foam of claim 1 in which the natural oil is a vegetable oil.
5. The flexible conventional polyurethane foam of claim 1 in which the natural oil is castor oil.
6. The flexible conventional polyurethane foam of claim 1 in which the natural oil is alkoxylated with ethylene oxide and one or more alkylene oxides chosen from propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, epichlorohydrin, cyclohexene oxide, styrene oxide, C 5 -C 30 α-alkylene oxides, polycarboxylic anhydrides and lactones.
7. The flexible conventional polyurethane foam of claim 1 in which the double metal cyanide (DMC) catalyst is a zinc hexacyanocobaltate.
8. The flexible conventional polyurethane foam of claim 1 in which the alkoxylated natural oil is capped with ethylene oxide.
9. The flexible conventional polyurethane foam of claim 4 in which the vegetable oil is capped with ethylene oxide.
10. The flexible conventional polyurethane foam of claim 1 in which the natural oil content of the alkoxylated natural oil polyol is at least 20% by weight.
11. The flexible conventional polyurethane foam of claim 1 in which the petroleum-based polyol is chosen from polyethers, polyesters, polyacetals, polycarbonates, polyesterethers, polyester carbonates, polythioethers, polyamides, polyesteramides, polysiloxanes, polybutadienes and polyacetones.
12. The flexible conventional polyurethane foam of claim 1 in which the petroleum-based polyol is a polyether polyol.
13. The flexible conventional polyurethane foam of claim 1 in which the sum of (a)+(b) is at least 40% but no greater than 50%.
14. A process for making a flexible conventional polyurethane foam comprising reacting:
at least one polyisocyanate; and
at least one natural oil alkoxylated in the presence of a double metal cyanide catalyst having
(a) an ethylene oxide content in the alkoxylated segment greater than 20% by weight,
(b) a primary hydroxyl group content of at least 10%, with the sum of (a)+(b) being at least 30% but no greater than 60%,
optionally at least one petroleum-based polyol,
in the presence of at least one of blowing agent and
optionally, a surfactant, pigment, flame retardant, catalyst or filler.
15. The process of claim 14 in which 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, isocyanate-terminated prepolymers and mixtures thereof.
16. The process of claim 14 in which the at least one polyisocyanate is toluene diisocyanate (TDI).
17. The process of claim 14 in which the natural oil is a vegetable oil.
18. The process of claim 14 in which the natural oil is castor oil.
19. The process of claim 14 in which the double metal cyanide (DMC) catalyst is a zinc hexacyanocobaltate.
20. The process of claim 14 in which the natural oil is alkoxylated with ethylene oxide and one or more alkylene oxides chosen from propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, epichlorohydrin, cyclohexene oxide, styrene oxide, C 5 -C 30 α-alkylene oxides, polycarboxylic anhydrides, lactones and mixtures thereof.
21. The process of claim 20 in which the natural oil is a vegetable oil.
22. The process of claim 20 in which the natural oil content of the alkoxylated natural oil polyol is at least 20% by weight.
23. The process of claim 14 in which the alkoxylated natural oil is capped with ethylene oxide.
24. The process of claim 14 in which the alkoxylated natural oil is an alkoxylated vegetable oil capped with ethylene oxide.
25. The process of claim 14 in which the petroleum-based polyol is chosen from polyethers, polyesters, polyacetals, polycarbonates, polyesterethers, polyester carbonates, polythioethers, polyamides, polyesteramides, polysiloxanes, polybutadienes and polyacetones.
26. The process of claim 14 in which the petroleum-based polyol is a polyether polyol.
27. The process of claim 14 in which the sum of (a)+(b) is at least 40% but no greater than 50%.