Alcohol adducts of N-heterocyclic carbenes: Latent catalysts for the thermally-controlled living polymerization of cyclic esters

Abstract

Alcohol adducts of the N-heterocyclic carbene, 1,3,4-triphenyl-4,5-dihydro-lff-l,2-triazol-5-ylidene (NHC), function as excellent single-component catalyst/initiators for the ring-opening polymerization of lactide and β-butyrolactone, Their reversible dissociation at elevated temperatures generates alcohol and triazolylidene carbene to provide a facile entry to polymerization of cyclic esters on demand. Under optimum conditions, adverse transesterification reactions are minimized, and importantly, upon complete consumption of monomer, a second monomer addition facilitates additional polymer growth, even after precipitation. Block copolymers were prepared by combining disparate polymerization techniques from the use of oligo-adducts and bifunctional initiators. Additionally, more complex polymer architectures were prepared from multifunctional or dendritic initiators, further demonstrating the versatility of the N-heterocyclic carbene platform. © 2006 American Chemical Society.