Synthesis of functional polyurethanes and polyesters from biomass-derived monomers
A method of making polyesters and polyurethanes from biomass-derived polyols. The polyol is biomass-derived and has the structure: wherein dashed bonds are single or double bonds and R is selected from the group consisting of —OH and ═O. Polyurethanes are made by reacting the polyol with a diisocyanate. Polyesters are made by reacting the polyol with a dicarboxylic acid.
1. A method of making biomass-derived polymers, the method comprising:
reacting a first polyol wherein the first polyol is biomass-derived and comprises a Formula I compound selected from the group consisting of:
wherein dashed bonds are single or double bonds and R is selected from ═O or —OH;
with a comonomer selected from the group consisting of a diisocyanate or a dicarboxylic acid for a time, and at a temperature to yield a polymeric product.
2. The method of claim 1 , wherein the diisocyanate is selected from the group consisting of methyldiphenyldiisocyanate, toluene diisocyanate, 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, and 4,4′-diisocyanato dicyclohexylmethane; and the dicarboxylic acid is selected from the group consisting of oxalic, malonic, succinic, glutaric, adipic, picric, phthalic, isophthalic, terephthalic, biphenyl-2,2′-dicarboxylic, and 2,6-naphthalenedicarboxylic acid acids.
3. The method of claim 1 , wherein, prior to reacting the first polyol with the diisocyanate or dicarboxylic acid, the first polyol is blended with a second polyol that is structurally distinct from the first polyol.
4. The method of claim 3 , wherein the second polyol is selected from the group consisting of linear or branched alkylene glycols, sugar alcohols, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, polybutadiene polyol, and polysulfide polyols.
5. The method of claim 3 , wherein the diisocyanate is selected from the group consisting of methyldiphenyldiisocyanate, toluene diisocyanate, 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, and 4,4′-diisocyanato dicyclohexylmethane; and the dicarboxylic acid is selected from the group consisting of oxalic, malonic, succinic, glutaric, adipic, picric, phthalic, isophthalic, terephthalic, biphenyl-2,2′-dicarboxylic, and 2,6-naphthalenedicarboxylic acid acids.
6. The method of claim 1 , wherein the first polyol comprises a Formula I compound where all the dashed bonds are double bonds and R is O.
7. The method of claim 6 , wherein the diisocyanate is selected from the group consisting of methyldiphenyldiisocyanate, toluene diisocyanate, 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, and 4,4′-diisocyanato dicyclohexylmethane; and the dicarboxylic acid is selected from the group consisting of oxalic, malonic, succinic, glutaric, adipic, picric, phthalic, isophthalic, terephthalic, biphenyl-2,2′-dicarboxylic, and 2,6-naphthalenedicarboxylic acid acids.
8. The method of claim 6 , wherein, prior to reacting the first polyol with the diisocyanate or dicarboxylic acid, the first polyol is blended with a second polyol that is structurally distinct from the first polyol.
9. The method of claim 8 , wherein the second polyol is selected from the group consisting of linear or branched alkylene glycols, sugar alcohols, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, polybutadiene polyol, and polysulfide polyols.
10. The method of claim 8 , wherein the diisocyanate is selected from the group consisting of methyldiphenyldiisocyanate, toluene diisocyanate, 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, and 4,4′-diisocyanato dicyclohexylmethane; and the dicarboxylic acid is selected from the group consisting of oxalic, malonic, succinic, glutaric, adipic, picric, phthalic, isophthalic, terephthalic, biphenyl-2,2′-dicarboxylic, and 2,6-naphthalenedicarboxylic acid acids.
11. The method of claim 1 , wherein the first polyol comprises:
12. The method of claim 11 , wherein the diisocyanate is selected from the group consisting of methyldiphenyldiisocyanate, toluene diisocyanate, 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, and 4,4′-diisocyanato dicyclohexylmethane; and the dicarboxylic acid is selected from the group consisting of oxalic, malonic, succinic, glutaric, adipic, picric, phthalic, isophthalic, terephthalic, biphenyl-2,2′-dicarboxylic, and 2,6-naphthalenedicarboxylic acid acids.
13. The method of claim 11 , wherein, prior to reacting the first polyol with the diisocyanate or dicarboxylic acid, the first polyol is blended with a second polyol that is structurally distinct from the first polyol.
14. The method of claim 13 , wherein the second polyol is selected from the group consisting of linear or branched alkylene glycols, sugar alcohols, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, polybutadiene polyol, and polysulfide polyols.
15. The method of claim 13 , wherein the diisocyanate is selected from the group consisting of methyldiphenyldiisocyanate, toluene diisocyanate, 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, and 4,4′-diisocyanato dicyclohexylmethane; and the dicarboxylic acid is selected from the group consisting of oxalic, malonic, succinic, glutaric, adipic, picric, phthalic, isophthalic, terephthalic, biphenyl-2,2′-dicarboxylic, and 2,6-naphthalenedicarboxylic acid acids.
16. The method of claim 11 , further comprising, prior to reacting the first polyol with the diisocyanate or dicarboxylic acid, reacting the first polyol with a maleimide, and N-substituted maleimides.
17. The method of claim 11 , wherein the diisocyanate is selected from the group consisting of methyldiphenyldiisocyanate, toluene diisocyanate, 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, and 4,4′-diisocyanato dicyclohexylmethane; and the dicarboxylic acid is selected from the group consisting of oxalic, malonic, succinic, glutaric, adipic, picric, phthalic, isophthalic, terephthalic, biphenyl-2,2′-dicarboxylic, and 2,6-naphthalenedicarboxylic acid acids.
18. The method of claim 11 , wherein, prior to reacting the first polyol with the diisocyanate or dicarboxylic acid, the first polyol is blended with a second polyol that is structurally distinct from the first polyol.
19. The method of claim 18 , wherein the second polyol is selected from the group consisting of linear or branched alkylene glycols, sugar alcohols, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, polybutadiene polyol, and polysulfide polyols.
20. The method of claim 18 , wherein the diisocyanate is selected from the group consisting of methyldiphenyldiisocyanate, toluene diisocyanate, 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, and 4,4′-diisocyanato dicyclohexylmethane; and the dicarboxylic acid is selected from the group consisting of oxalic, malonic, succinic, glutaric, adipic, picric, phthalic, isophthalic, terephthalic, biphenyl-2,2′-dicarboxylic, and 2,6-naphthalenedicarboxylic acid acids.
21. The method of claim 1 , wherein the first polyol comprises:
22. The method of claim 21 , wherein the diisocyanate is selected from the group consisting methyldiphenyldiisocyanate, toluene diisocyanate, 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, and 4,4′-diisocyanato dicyclohexylmethane; and the dicarboxylic acid is selected from the group consisting of oxalic, malonic, succinic, glutaric, adipic, picric, phthalic, isophthalic, terephthalic, biphenyl-2,2′-dicarboxylic, and 2,6-naphthalenedicarboxylic acid acids.
23. The method of claim 21 , wherein, prior to reacting the first polyol with the diisocyanate or dicarboxylic acid, the first polyol is blended with a second polyol that is structurally distinct from the first polyol.
24. The method of claim 23 , wherein the second polyol is selected from the group consisting of linear or branched alkylene glycols, sugar alcohols, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, polybutadiene polyol, and polysulfide polyols.
25. The method of claim 23 , wherein the diisocyanate is selected from the group consisting of methyldiphenyldiisocyanate, toluene diisocyanate, 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, and 4,4′-diisocyanato dicyclohexylmethane; and the dicarboxylic acid is selected from the group consisting of oxalic, malonic, succinic, glutaric, adipic, picric, phthalic, isophthalic, terephthalic, biphenyl-2,2′-dicarboxylic, and 2,6-naphthalenedicarboxylic acid acids.
26. The method of claim 1 , wherein the first polyol comprises:
27. The method of claim 26 , wherein the diisocyanate is selected from the group consisting of methyldiphenyldiisocyanate, toluene diisocyanate, 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, and 4,4′-diisocyanato dicyclohexylmethane; and the dicarboxylic acid is selected from the group consisting of oxalic, malonic, succinic, glutaric, adipic, picric, phthalic, isophthalic, terephthalic, biphenyl-2,2′-dicarboxylic, and 2,6-naphthalenedicarboxylic acid acids.
28. The method of claim 26 , wherein, prior to reacting the first polyol with the diisocyanate or the dicarboxylic acid, the first polyol is blended with a second polyol that is structurally distinct from the first polyol.
29. The method of claim 28 , wherein the second polyol is selected from the group consisting of linear or branched alkylene glycols, sugar alcohols, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, polybutadiene polyol, and polysulfide polyols.
30. The method of claim 28 , wherein the diisocyanate is selected from the group consisting of methyldiphenyldiisocyanate, toluene diisocyanate, 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, and 4,4′-diisocyanato dicyclohexylmethane; and the dicarboxylic acid is selected from the group consisting of oxalic, malonic, succinic, glutaric, adipic, picric, phthalic, isophthalic, terephthalic, biphenyl-2,2′-dicarboxylic, and 2,6-naphthalenedicarboxylic acid acids.
31. A polymer comprising
a first co-monomer comprising a diisocyanate or a dicarboxylic acid; and
a second co-monomer which, prior to polymerization, comprises a compound of Formula I:
wherein dashed bonds are single or double bonds and R is selected from ═O or —OH.
32. The polymer of claim 31 , wherein the first co-monomer comprises a diisocyanate.
33. The polymer of claim 31 , wherein the first co-monomer comprises a dicarboxylic acid.
34. A polymer made by the method of claim 1 .
35. A polymer made by the method of claim 16 .