Fillers are widely used to improve the thermomechanical response of polymer matrices, yet often in an unpredictable manner because the relationships between the mechanical properties of the composite material and the primary (chemical) structure of its molecular components have remained elusive so far. Here, we report on a combined theoretical and experimental study of the structural and thermomechanical properties of carbon nanotube (CNT)-reinforced polybenzoxazine resins, as prepared from two monomers that only differ by the presence of two ethyl side groups. Remarkably, while addition of CNT is found to have no impact on the glass-transition temperature ( Tg) of the ethyl-decorated resin, the corresponding ethyl-free composite features a surge by ∼47 °C (50 °C) in Tg, from molecular dynamics simulations (dynamic mechanical analysis measurements), as compared to the neat resin. Through a detailed theoretical analysis, we propose a microscopic picture for the differences in the thermomechanical properties of the resins, which sheds light on the relative importance of network topology, cross-link and hydrogen-bond density, chain mobility, and free volume.
Keywords: CNT nanocomposite; benzoxazine thermoset; chain mobility; network topology; thermomechanical stability.