Irreversible Ring-Opening Polymerization: Harnessing the Thermodynamics of Strainless Monomers

Ring-opening polymerization (ROP) represents a powerful tool for synthesizing functional polymers, distinguished by its exceptional control over polymerization processes and the facile incorporation of diverse backbone functionalities.However, ROP of strainless monomers remains challenging due to their unfavorable thermodynamics.To address this limitation, irreversible ROP that substantially shifts the equilibrium towards polymerization by introducing additional thermodynamically favorable processes has emerged as a versatile and innovative approach.This minireview highlights representative examples of irreversible ROP from three strategies: (1) ROP driven by functional group transformation/isomerization; (2) ROP driven by gas molecule liberation; (3) alternating ROP (AROP), with an emphasis on the design principle and reaction mechanism.It is anticipated that these discussions will provide valuable insights into irreversible ROP.