Thermally Healable Polyurethanes Based on Furfural-Derived Monomers via Baylis-Hillman Reaction

Abstract

Two novel acrylate monomers with diol group, 2-hydroxyethyl 2-(furan-2-yl(hydroxy)methyl)acrylate and methyl 2-(hydroxy(5-(hydroxymethyl)furan-2-yl)methyl)acrylate, were synthesized via Baylis-Hillman reaction in moderate yields. The monomer 2-hydroxyethyl 2-(furan-2-yl(hydroxy)methyl)acrylate was obtained from furfural and 2-hydroxyethyl acrylate (HEA); methyl 2-(hydroxy[5-(hydroxymethyl)furan-2-yl)methyl)acrylate was prepared from 5-hydroxymethl furfural (HMF) and methyl acrylate. The monomer 2-hydroxyethyl 2-(furan-2-yl(hydroxy)methyl)acrylate reacted with toluene diisocyanate (TDI)-derived or hexamethylene diisocyanate (HDI)-derived diisocyanate oligomers to obtain the corresponding linear polyurethane oligmers PU-1T and PU-1H. Similarly, the diol methyl 2-(hydroxy(5-(hydroxymethyl)furan-2-yl)methyl)acrylate reacted with TDI- or HDI-derived diisocyanate oligomers to obtain the corresponding linear polyurethane oligmers PU-2T and PU-2H. The number-average molecular weights of the linear polyurethane oligomers are approximately 300–350 Da. There are furan groups in the linear polyurethane oligomers PU-1T, PU-1H, PU-2T and PU-2H, which makes them capable of undergoing reversible Diels-Alder reaction with 4,4′-bismaleimidodiphenylmethane (BMI) to form the corresponding crosslinked polyurethanes CPU-1T, CPU-1H, CPU-2T and CPU-2H. Pencil hardness of CPU-1T, CPU-1H, CPU-2T and CPU-2H are 3H, 2H, 2H and HB, respectively. Glass transition temperatures of CPU-1T, CPU-1H, CPU-2T and CPU-2H are 104.8, 97.6, 5.1 and 1.2 °C, respectively. TGA analysis shows that Td90 values of the CPUs range from 180 to 250 °C. Furthermore, the reversible crosslinked polyurethanes CPU-1T and CPU-1H can be completely self-healed at 90 °C for 3 h, while CPU-2T and CPU-2H can self-heal at 80 °C for 3 h presumably due to their low glass transition temperatures.