Easily Processable Thermosets with Outstanding Performance via Smart Twisted Small-Molecule Benzoxazines.

High-performance aromatic polymers have excellent thermal, mechanical, and electrical properties and are lightweight, but it is highly challenging to deliver outstanding performances while still maintaining good processability of the precursors. Here, a new family of small-molecule benzoxazine resins with ortho-maleimide functionality is reported, which strikes an exceptional balance between the processability and performance. The excellent processability is attributed to the twisted molecular configurations of ortho-maleimide-substituted benzoxazines, which prevent intermolecular packing in the resin systems. The new benzoxazines can polymerize through multiple routes, which eliminate the twisted structures and create highly cross-linked polymer networks. The resulting new polymers are found to possess fascinating properties such as a high thermal stability (no Tg can be detected before 400 °C), excellent flame retardancy (a heat release capacity of 42.5 J g-1 K-1 ), and low dielectric constants (2.62-2.30 in the frequency range of 1 Hz to 10 MHz). The combined processability and versatility highlight the potential of smart benzoxazines in the preparation of high-performance thermosets, with important new applications that may span aerospace, transportation, and electronic packaging materials.