Reprocessable polyhydroxyurethane networks reinforced with reactive polyhedral oligomeric silsesquioxanes (POSS) and exhibiting excellent elevated temperature creep resistance

Abstract

The rapid development of covalent adaptable networks or vitrimers shows promise for addressing the long-standing recycling issues associated with conventional, permanently cross-linked thermosets. At the same time, it is important to demonstrate that properties of reprocessable polymer networks can be optimized to meet the ongoing demand for high-performance materials. We have fabricated reprocessable polyhydroxyurethane (PHU) network composites reinforced with reactive polyhedral oligomeric silsesquioxanes (POSS). With functionalized POSS serving as a fraction of the cross-linkers, the PHU–POSS network nanocomposites exhibit significantly enhanced storage modulus at the rubbery plateau region relative to the neat PHU network. With up to 10 wt% POSS loading, these network composites can undergo melt-state reprocessing at 140 °C with 100% property recovery associated with cross-link density. We also show that hydroxyurethane dynamic chemistry leads to excellent creep resistance at elevated temperature up to 90 °C and is unaffected by reactive incorporation of POSS. This study demonstrates the effectiveness of POSS as nanofillers for designing high-performance, organic−inorganic dynamic PHU networks with excellent reprocessability. • Dynamic PHU–POSS network composites are made with up to 10 wt% reactive POSS. • PHU–POSS network composites can be melt-reprocessed with 100% recovery of cross-link density. • Improved thermal stability and rubbery plateau modulus relative to the neat PHU network. • Excellent elevated-temperature creep resistance comparable to static networks.