Mechanism of the Polymerization of rac-Lactide by Fast Zinc Alkoxide Catalysts

The ring-opening transesterification polymerization (ROTEP) of rac-lactide (rac-LA) using L^XZn catalysts (L^X = ligand having phenolate, amine, and pyridine donors with variable para substituents X on the bound phenolate donor; X = NO₂, Br, t-Bu, OMe) was evaluated through kinetics experiments and density functional theory, with the aim of determining how electronic modulation of the ligand framework influences polymerization rate, selectivity, and control. After determination that zinc-ethyl precatalysts required 24 h of reaction with benzyl alcohol to convert to active alkoxide complexes, the subsequently formed species proved to be active and fairly selective, polymerizing up to 300 equiv of rac-LA in 6-10 min while yielding isotactic (P_m = 0.72-0.78) polylactide (PLA) with low dispersities: = 1.06-1.17. In contrast to previous work with aluminum catalysts for which electronic effects of ligand substituents were significant (Hammett ρ = +1.2-1.4), the L^XZn systems exhibited much less of an effect (ρ = +0.3). Density functional calculations revealed details of the initiation and propagation steps, enabling insights into the high isotacticity and the insensitivity of the rate on the identity of X.