Utilizing bio‐derived amine‐terminated thermoplastic polyhydroxyurethanes as crosslinkers for hybrid thermosets

Abstract

AbstractBio‐sourced amine‐terminated polyhydroxyurethanes (PHUs) are obtained by terpolymerizing bio‐based diglycerol dicarbonate (DGC) or mannitol biscarbonate (MBC) with Priamine 1074 and 1,10‐diaminodecane (DAD). Partially bio‐based thermoset non‐isocyanate polyurethane (NIPU) hybrids with high biorenewable carbon content (84%–95%) are obtained by using the synthesized PHUs as crosslinkers with cyclic carbonated copolymers derived from epoxy‐functional templates. The latter are derived from the atom transfer radical polymerization (ATRP) of an alkyl methacrylate (C13MA, with an average side‐chain length of 13) and epoxy‐functional glycidyl methacrylate (GMA) mixtures (initial GMA mol fraction = 0.1–0.3). By manipulating template functionality as well as type of crosslinker, crosslinked NIPU hybrids are achieved with Young's moduli ranging from 2.35 ± 0.45 to 20.85 ± 1.73 MPa for DGC‐based crosslinkers and 1.24 ± 0.61 to 6.45 ± 1.05 MPa for MBC‐based ones. Moreover, with increased density of urethane linkages, networks become tighter as measured by swelling ratios (SR) of the networks in tetrahydrofuran (THF), consistent with the estimated molecular weight between crosslinks obtained rheologically. The crosslinked NIPUs display high conversions, ranging from 75% to 95%, despite being solvent‐ or catalyst‐free systems.