Unexpected Healability of an ortho-Blocked Polybenzoxazine Resin

Ring-opening polymerization of bifunctional benzoxazine has long been thought to produce a permanent network structure without reprocessing ability. Here, we demonstrate that surprising healability can be achieved by a controlled polymerization of an ortho-blocked bifunctional benzoxazine poly(oC-hda). The cured resin possesses a cross-linked structure, but can be deformed, remolded from crushed pieces or healed from mechanical damage. Based on a series of intensive experiments, we show that the healability can be explained by a dynamic bonding exchange mechanism between the phenoxy structures existing during the curing process. Moreover, we verify the possibility to heal the fatigue damaged poly(oC-hda) based composite to extend its service life. Our study provides another dynamic covalent bond to synthesize healable polymers, offering a broad platform for combining healability and desired thermosetting features together.