Thermally reprocessable bio-based polyhydroxyurethane vitrimers

Abstract

Vitrimers present one way to address growing demand for sustainably sourced, recyclable thermoset polyhydroxyurethanes (PHUs). We employ vinylogous urethane formation for dynamic bonding, using amine-terminated bio-sourced PHUs (prepared via terpolymerization of diglycerol dicarbonate (DGC) with Priamine 1074 and 1,10-diaminodecane (DAD)) as crosslinkers with ketone-functional copolymers. The latter are synthesized via atom transfer radical copolymerization (ATRP) of an alkyl methacrylate (C13MA, with average side-chain length of 13 carbons) with (2-acetoacetoxy) ethyl methacrylate (AAEMA) (initial AAEMA mole fraction = 0.1–0.4). By manipulating copolymer functionality, thermoset PHUs (Young's moduli spanning from 31 ± 1.5 kPa to 133 ± 5.7 kPa) are obtained. Furthermore, as ketone group concentration increases, networks became tighter, with slower relaxation rates and increased apparent activation energy of stress relaxation, in agreement with calculated molecular weight between crosslinks obtained rheologically. Finally, thermoset PHUs can be effectively recycled three times through remolding at 100 °C without compromising their mechanical properties.