Polyurethanes Synthesized with Blends of Polyester and Polycarbonate Polyols-New Evidence Supporting the Dynamic Non-Covalent Exchange Mechanism of Intrinsic Self-Healing at 20 °C.

Abstract

Polyurethanes (PUs) synthesized with blends of polycarbonate and polyester polyols (CD+PEs) showed intrinsic self-healing at 20 °C. The decrease in the polycarbonate soft segments content increased the self-healing time and reduced the kinetics of self-healing of the PUs. The percentage of C-O species decreased and the ones of C-N and C=O species increased by increasing the polyester soft segments in the PUs, due to higher micro-phase separation. All PUs synthetized with CD+PE blends exhibited free carbonate species and interactions between the polycarbonate and polyester soft segments to a somewhat similar extent in all PUs. By increasing the polyester soft segments content, the storage moduli of the PUs decreased and the tan delta values increased, which resulted in favored polycarbonate soft segments interactions, and this was related to slower kinetics of self-healing at 20 °C. Although the PU made with a mixture of 20 wt.% CD and 80 wt.% PE showed cold crystallization and important crystallinity of the soft segments, as well as high storage moduli, the intercalation of a small amount of polycarbonate soft segments disturbed the interactions between the polyester soft segments, so it exhibited self-healing at 20 °C. The self-healing of the PUs was attributed to the physical interactions between polycarbonate soft segments themselves and with polyester soft segments, and, to a minor extent, to the mobility of the polymeric chains. Finally, the PUs made with 40 wt.% or more polyester polyol showed acceptable mechanical properties.