Fundamental understanding of fluorophenol-derived dual organocatalysts for ring-opening polymerization of lactide†

Designing benign catalytic systems is essential to accelerate polymerization research. This requires a thorough understanding of structural interactions between catalysts and monomers. We here report a combined approach involving bench experiments, density functional theory (DFT), and multivariate linear regression (MLR) to elucidate the structure–activity relationships of catalysts. Fluorophenol derived dual organocatalysts were designed and applied for ring-opening polymerization (ROP) of L-lactide (LLA), where the catalytic system exhibits high catalytic activity in bulk at 140 °C. Mechanistic studies revealed a synergistic catalytic process, where the dual organocatalysts activate the initiator and monomer through hydrogen bonding interaction. By applying a multivariate linear regression (MLR) model, the study identifies key electronic and thermodynamic descriptors that significantly influence the observed rate constants (k_obs) in the catalytic process.