Intramolecularly Self-Activated Degradable Aromatic Polyesters Inspired by RNA Autohydrolysis

Abstract The long-term persistence of conventional aromatic polyesters remains a major challenge for polymer sustainability. Inspired by RNA autohydrolysis, we developed two self-activated degradable aromatic polyesters, poly(2,2-ethyl carboxylate-1,3-propanediol terephthalate) (PEPT) and poly(2,2-ethyl carboxylate-1,3-propanediol furan diester) (PEPF), by introducing hydrolytically labile aliphatic ester groups as pendant activation sites. Preferential hydrolysis of these side-chain ester groups increases polymer hydrophilicity and facilitates subsequent cleavage of the aromatic polyester backbone, enabling a self-accelerating degradation process. PEPT and PEPF undergo complete apparent mass loss within 7 h in 1 M NaOH at 37 °C and degrade within 6 months in a 5 wt % aqueous disodium hydrogen phosphate solution at 58 °C. Meanwhile, both polymers retain the characteristic thermal properties and processability of aromatic polyesters. This work establishes a molecular design strategy for imparting hydrolytic degradability to aromatic polyesters through internally activated side-chain chemistry.