First Example of N-Heterocyclic Carbenes as Catalysts for Living Polymerization: Organocatalytic Ring-Opening Polymerization of Cyclic Esters

Abstract

A novel metal-free, organocatalytic approach to living polymerization is presented. N-heterocyclic carbenes were employed as nucleophilic catalysts for the ring-opening polymerization (ROP) of cyclic ester monomers. The catalysts is used in combination with an initiator, such as an alcohol, which generates an α-end group bearing the ester from the initiating alcohol upon ring-opening and a hydroxyl functional ω-chain end that propagates the chain. This class of catalyst proved to be more reactive than tertiary amine and phosphine nucleophiles, producing narrowly dispersed polymers of predictable molecular weights at room temperature in 1−2 h. Catalysis with respect to both initiating alcohol and monomer was observed. Control of the α and ω end-groups was demonstrated with a pyrene-labeled initiator, allowing the preparation of well-defined macromolecular architectures. Analogous to the ROP of cyclic esters using biocatalysts, the polymeriztion pathway using the N-heterocyclic carbenes is believed to ensue through a monomer-activated mechanism.