Aliphatic polyesters are promising polymeric materials because they use hydroxy acids as biocompatible and renewable monomer sources, and can access hydrolytic biodegradation pathways at high pH and temperature. The β-diketiminate (BDI or NacNac) class of ligand frameworks are privileged for these transformations because they can stabilize low valent metals via electron donation and have tunable R groups on each of the nitrogen atoms. Zn catalysts supported by NacNac ligands have shown high activity in the ring-opening polymerization (ROP) of lactide (LA) and β-butyrolactone (BBL), along with the ring-opening copolymerization (ROCOP) of cyclohexene oxide and CO2 (CHO/CO2). Early work by Coates and coworkers uncovered distinct structure-function relationships within the ligand backbone and aryl substituents, and suggest a fine balance between steric protection and accessibility is critical for high catalyst activity. Despite their distinct differences in steric and electronic functionality, alkyl substituted NacNac frameworks have received limited attention, while initial reports indicate enhanced susceptibility to ligand redistribution which can limit catalyst activity. In this work, we have synthesized aryl/alkyl derivatives and investigated their reactivity in the mechanistically distinct LA, BBL, and CHO/CO2 polymerizations. Structure-function relationships of the Zn catalysts in these polymerization reactions will be discussed in the context of future ligand and catalyst design.

Balancing reactivity and stability: Aryl/alkyl beta-diketiminate (NacNac) zinc catalysts for ring-opening and ring-opening copolymerization

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.