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.