High strength polyurethane foam compositions and methods
Disclosed are high strength polyurethane foam compositions and methods of making them. In one aspect, the inventive polyurethane foams include strength enhancing additives comprising one or more polycarbonate polyols derived from the copolymerization of CO 2 and one or more epoxides. In one aspect, the inventive methods include the step of substituting a portion of the polyether polyol in the B-side of a foam formulation with one or more polycarbonate polyols derived from the copolymerization of CO 2 and one or more epoxides.
1. A method for increasing the strength of a polyurethane foam composition, the foam composition comprising the reaction product of a polyol component and a polyisocyanate component, the method comprising the step of incorporating into the polyol component a polycarbonate polyol derived from the copolymerization of one or more epoxides and carbon dioxide, wherein the polycarbonate polyol is added in a quantity from about 2 weight percent to about 50 weight percent, from about 5 weight percent to about 25 weight percent, from about 2 weight percent to about 10 weight percent, from about 10 weight percent to about 20 weight percent, from about 20 weight percent to about 30 weight percent, or from about 30 weight percent to about 50 weight percent of all polyols present in the polyol component;
wherein a tear strength value measured by ASTM D 3574-08 of the foam composition comprising the added polycarbonate polyol is greater than the tear strength value of a corresponding foam composition formulated without the added polycarbonate polyol.
2. The method of claim 1 , wherein the polyol component comprises one or more polyols selected from the group consisting of polyether polyols, polyester polyols, aliphatic polyols, and mixtures of any two or more of these.
3. The method of claim 2 , wherein the polyol component comprises polyether polyol.
4. The method of claim 1 , wherein the tear strength value of the foam composition comprising the added polycarbonate polyol is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, or at least 100% greater than the tear strength value of the corresponding foam composition formulated without the added polycarbonate polyol.
5. The method of claim 1 , wherein the tear strength values are normalized for density of the foam compositions being compared.
6. The method of claim 1 , wherein the foam compositions are formulated such that the foam composition comprising the added polycarbonate polyol and the corresponding foam composition formulated without the added polycarbonate polyol have the same density.
7. The method of claim 1 , wherein the foam composition comprises flexible polyurethane foam, or wherein the foam composition comprises viscoelastic polyurethane foam, or wherein the foam composition comprises rigid polyurethane foam.
8. The method of claim 1 , wherein the density measured according to ASTM D3574 of the foam composition comprising the added polycarbonate polyol is less than the density of the corresponding foam composition formulated without the added polycarbonate polyol, and wherein the tear strength value measured according to ASTM D3574-08 of the foam composition comprising the added polycarbonate polyol is greater than the tear strength value of the corresponding foam composition formulated without the added polycarbonate polyol.
9. The method of claim 8 , wherein the density of the foam composition comprising the added polycarbonate polyol is at least 10%, at least 20%, at least 30%, at least 40% or at least 50% less than the density of the corresponding foam composition formulated without the added polycarbonate polyol.
10. The method of claim 8 , wherein the tear strength value of the foam composition comprising the added polycarbonate polyol is at least 10%, at least 20%, at least 30%, at least 40% or at least 50% greater than the tear strength value of the corresponding foam composition formulated without the added polycarbonate polyol.
11. The method of claim 1 , wherein the polycarbonate polyol contains a primary repeating unit having a structure:
where R 1 , R 2 , R 3 , and R 4 are, at each occurrence in the polymer chain, independently selected from the group consisting of —H, fluorine, an optionally substituted C 1-40 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, and an optionally substituted aryl group, where any two or more of R 1 , R 2 , R 3 , and R 4 may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms.
12. The method of claim 11 , wherein the polycarbonate polyol contains a primary repeating unit having a structure:
13. The method of claim 12 , wherein R 1 is, at each occurrence in the polymer chain, independently —H, or —CH 3 .
14. The method of claim 11 , wherein the polycarbonate polyol is characterized in that it has an Mn between about 500 g/mol and about 20,000 g/mol, between about 1,000 g/mol and about 5,000 g/mol, between about 1,000 g/mol and about 3,000 g/mol, or between about 1,000 g/mol and about 3,000 g/mol, or an Mn of about 1,000 g/mol, about 1,200 g/mol, about 1,500 g/mol, about 2,000 g/mol, about 2,500 g/mol or about 3,000 g/mol.
15. The method of claim 11 , wherein the aliphatic polycarbonate polyol is characterized in that more than 98%, more than 99%, or more than 99.5% of the chain ends are groups reactive toward isocyanate.
16. The method of claim 15 , wherein the chain ends reactive toward isocyanate comprise —OH groups.
17. A polyurethane foam composition comprising the reaction product of a polyol component and a polyisocyanate component, wherein the polyol component comprises a polycarbonate polyol derived from the copolymerization of one or more epoxides and carbon dioxide, wherein the polycarbonate polyol is present in a quantity from about 2 weight percent to about 50 weight percent, from about 5 weight percent to about 25 weight percent, from about 2 weight percent to about 10 weight percent, from about 10 weight percent to about 20 weight percent, from about 20 weight percent to about 30 weight percent, or from about 30 weight percent to about 50 weight percent of all polyols present in the polyol component and characterized in that a tear strength value measured according to ASTM D 3574-08 of the foam composition comprising the added polycarbonate polyol is greater than the tear strength value of a corresponding foam composition formulated without the added polycarbonate polyol.
18. The polyurethane foam composition of claim 17 , wherein the polyol component comprises one or more polyols selected from the group consisting of polyether polyols, polyester polyols, aliphatic polyols, and mixtures of any two or more of these.
19. The polyurethane foam composition of claim 18 , wherein the polyol component comprises polyether polyol.
20. The polyurethane foam composition of claim 17 , wherein the tear strength value of the foam composition comprising the polycarbonate polyol is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, or at least 100% greater than the tear strength value of the corresponding foam composition formulated without the added polycarbonate polyol.
21. The polyurethane foam composition of claim 20 , wherein the tear strength values are normalized for density of the foam compositions being compared.
22. The polyurethane foam composition of claim 20 , wherein the foam composition is formulated such that the foam composition comprising the added polycarbonate polyol and the corresponding foam composition formulated without the added polycarbonate polyol have the same density.
23. The polyurethane foam composition of claim 17 , wherein the foam composition comprises flexible polyurethane foam or wherein the foam composition comprises viscoelastic polyurethane foam, or wherein the foam composition comprises rigid polyurethane foam.
24. The polyurethane foam composition of claim 17 , wherein the density measured according to ASTM D3574-08 of the foam composition comprising the polycarbonate polyol is less than the density of the corresponding foam composition formulated without the polycarbonate polyol.
25. The polyurethane foam composition of claim 24 , wherein the density of the foam comprising the polycarbonate polyol is at least 10%, at least 20%, at least 30%, at least 40% or at least 50% less than the density of the corresponding foam composition formulated without the added polycarbonate polyol.
26. The polyurethane foam composition of claim 24 , wherein the measured tear strength value is at least 10%, at least 20%, at least 30%, at least 40% or at least 50% greater than the tear strength value of the corresponding foam composition formulated without the polycarbonate polyol.
27. The polyurethane foam composition of claim 17 , wherein the polycarbonate polyol contains a primary repeating unit having a structure:
where R 1 , R 2 , R 3 , and R 4 are, at each occurrence in the polymer chain, independently selected from the group consisting of —H, fluorine, an optionally substituted C 1-40 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, and an optionally substituted aryl group, where any two or more of R 1 , R 2 , R 3 , and R 4 may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms.
28. The polyurethane foam composition of claim 27 , wherein the polycarbonate polyol contains a primary repeating unit having a structure:
29. The polyurethane foam composition of claim 28 , wherein R 1 is, at each occurrence in the polymer chain, independently —H, or —CH 3 .
30. The polyurethane foam composition of claim 27 , wherein the polycarbonate polyol is characterized in that it has an Mn between about 500 g/mol and about 20,000 g/mol, between about 1,000 g/mol and about 5,000 g/mol, or between about 1,000 g/mol and about 3,000 g/mol, or an Mn of about 1,000 g/mol, about 1,200 g/mol, about 1,500 g/mol, about 2,000 g/mol, about 2,500 g/mol or about 3,000 g/mol.
31. The polyurethane foam composition of claim 30 , wherein the polycarbonate polyol is characterized in that more than 98%, more than 99%, or more than 99.5% of the chain ends are groups reactive toward isocyanate.
32. The polyurethane foam composition of claim 31 , wherein the chain ends reactive toward isocyanate comprise OH groups.
33. The method of claim 1 , wherein the polycarbonate polyol is characterized in that, on average in the composition, the percentage of carbonate linkages is 85% or greater.
34. The method of claim 33 , wherein the polycarbonate polyol is characterized in that, on average in the composition, the percentage of carbonate linkages is 90% or greater.
35. The method of claim 34 , wherein the polycarbonate polyol is characterized in that, on average in the composition, the percentage of carbonate linkages is 95% or greater.
36. The method of claim 35 , wherein the polycarbonate polyol is characterized in that, on average in the composition, the percentage of carbonate linkages is 98% or greater.
37. The method of claim 36 , wherein the polycarbonate polyol is characterized in that, on average in the composition, the percentage of carbonate linkages is 99% or greater.
38. The polyurethane foam composition of claim 17 , wherein the polycarbonate polyol is characterized in that, on average in the composition, the percentage of carbonate linkages is 85% or greater.
39. The polyurethane foam composition of claim 38 , wherein the polycarbonate polyol is characterized in that, on average in the composition, the percentage of carbonate linkages is 90% or greater.
40. The polyurethane foam composition of claim 39 , wherein the polycarbonate polyol is characterized in that, on average in the composition, the percentage of carbonate linkages is 95% or greater.
41. The polyurethane foam composition of claim 40 , wherein the polycarbonate polyol is characterized in that, on average in the composition, the percentage of carbonate linkages is 98% or greater.
42. The polyurethane foam composition of claim 41 , wherein the polycarbonate polyol is characterized in that, on average in the composition, the percentage of carbonate linkages is 99% or greater.