Zwitterionic polymerization: A kinetic strategy for the controlled synthesis of cyclic polylactide

Abstract

The zwitterionic ring-opening polymerization of lactide initiated by ?/-heterocyclic carbenes generates cyclic polylactides with well-defined molecular weights between Mn = 5000 and 30 000 g/mol with narrow polydispersities (Mw/Mn = 1.31). These zwitterionic polymerizations are extremely rapid {kp = 48.7 M-1 s-1), but also exhibit exceptional control of molecular weight and molecular weight distribution. The unusual kinetic features of these zwitterionic polymerizations are illuminated with kinetic and mechanistic investigations, which implicate a mechanism that involves a slow initiation step (second order in [M]), a propagation step (first order in [M]) that is much faster than initiation {kl = 0.274 M-2 s-1), cyclization {kc = 0.0575 s-1), and depropagation (kd = 0.208 s-1). Numerical and stochastic simulations of the kinetic data provide a kinetic rationale for the evolution of molecular weight with monomer conversion: the molecular weights increase with increasing monomer conversion, exhibit a nonzero intercept near 0% monomer conversion, and are relatively insensitive to the initial monomer-to-initiator ratio. The observed narrow molecular weight distributions are due to a high rate of propagation relative to cyclization and chain transfer. Kinetic simulations define the kinetic criteria under which the active zwitterions remain in solution; these simulations were substantiated by chain-extension experiments, which provide experimental evidence for chain extension of the zwitterions and reinitiation by the ?/-heterocyclic carbenes liberated upon macrocyclization. The kinetic model rationalizes some of the unique features of zwitterionic ring-opening polymerization and provides a useful mechanistic framework to optimize these polymerizations as a strategy to generate well-defined cyclic polyesters. © 2009 American Chemical Society.