Ultrarapid Cerium(III)–NHC Catalysts for High Molar Mass Cyclic Polylactide
Ryan W. F. Kerr, Paul M. D. A. Ewing, Sumesh K. Raman, Andrew D. Smith, Charlotte K. Williams, Polly L. Arnold
Abstract
Cyclic polyesters could improve the properties of degradable plastics, but routes to them that provide a product with faster rates, higher molar mass, and greater selectivity for cyclic vs linear polymer are needed. Here, homogeneous Ce(III)–N-heterocyclic carbene (NHC) catalysts show outstanding activities (turn-over-frequency (TOF) > 864 000 h–1), excellent control, and selectivity for cyclic polylactide (PLA) topology (>95%), yielding high molar mass PLA (60 < Mn < 250 kg mol–1). They efficiently produce cyclic PLA from rac-lactide or l-lactide and aliphatic cyclic polyesters from ε-caprolactone or β-butyrolactone. The enhanced performances are only achievable from combining cooperative Lewis acidic cerium(III) and hemilabile N-heterocyclic carbene functionalities.