Fabrication of In Situ Nanofiber-Reinforced Molecular Composites by Nonequilibrium Self-Assembly

Although the concept of molecular composites (MCs) is very promising, there are major obstacles arising from the immiscibility of the rigid-rod with the random-coil polymers. Here, we developed a novel method for fabricating an in situ reinforced MC system with nonequilibrium self-assembled nanofibrous structures based on bisphenol A epoxy resin, 4,4'-diaminodiphenylsulfone, bismaleimide, and a polyphenylene ether (PPO) oligomer. A variety of spectroscopic and morphological techniques were used to probe the structural evolution from the emergence of nanofibrils, to growth and aggregation of nanofibers, and then to the formation of in situ reinforced MC with strong interfacial interactions. The in situ nanofibers within the polymer matrix could be formed by the polymerization force extruding the PPO phase through the interspaces within the simultaneous interpenetrating network polymers during the cure process of the thermosetting resin system. Compared to the control sample, the in situ nanofiber-reinforced MC exhibited better thermal properties and flame retardancy. In particular, the obtained MC showed a significant improvement in glass transition temperature and mechanical properties, which were mainly attributed to the restriction of high thermal stability of PPO on the segmental motion of polymer chains, the toughening and reinforcement behaviors of PPO nanofibers on the matrix, and the chemical interaction at the PPO/matrix interface.