Fire‐Safe Polyesters Enabled by End‐Group Capturing Chemistry

Upon heating, polyesters decompose to small molecules and release flammable volatiles and toxic gases, primarily through chain scission of their ester linkages, and therefore exhibit poor fire‐safety properties, thus restricting their applications. Reported herein is an end‐group‐capturing effect of (bis)oxazoline groups, generated from the thermal rearrangement of the N‐(2‐hydroxyphenyl)phthalimide (HPI) moiety which was incorporated into the polyester chain by copolymerization. These copolyesters, as a result, exhibit high efficiency in retarding decomposition by capturing the decomposed products, particularly for the carbonyl‐terminated fragments, thus increasing the fire‐safety properties, such as self‐extinguishing, anti‐dripping, and inhibiting heat release and smoke production. The successful application of this method in both semi‐aromatic and aliphatic polyesters provide promising perspectives to designing versatile fire‐safe polymers. Captured: End‐group capture of benzoxazole from the thermal rearrangement of a hydroxy‐containing phthalimide group contributes to the fire‐safety features of polyesters. This novel strategy exhibits applicability and efficiency for both semi‐aromatic and aliphatic polyesters, providing a new design approach to fire‐safe polymers.