Polyesters are an important class of polymers due to their biodegradability, mechanical properties, and use in biomedical applications. These polymers are often synthesized in industrially intensive processes via polycondensation or ring-opening polymerizations; this wastes chemicals and limits structural diversity. It is therefore desirable to develop new synthetic routes from inexpensive, abundant, and renewable feedstocks. This research explores the development of novel bimetallic main group/group 10 catalytic systems that are capable of copolymerizing olefins and carbon dioxide (CO2) to produce polyesters. Currently, there are no catalytic processes that can sequentially add substrates into metal-carbon bonds and then metal-oxygen bonds. However, late transition metal catalysts are known to polymerize ethylene efficiently, while main group alkyl compounds are known chain transfer agents, many of which are capable of inserting CO2 into metal-carbon bonds. Fundamental studies into intermolecular polymeryl chain transfer to main group elements and alkene carboxylation have identified suitable polymerization and chain transfer metals. Using these metals, bimetallic complexes have been synthesized and used as cooperative catalysts for ethylene and carbon dioxide copolymerization. By developing specialized heterobimetallic catalysts, a structurally diverse range of polyesters can be synthesized from inexpensive and abundant starting materials. The study of the fundamental reactivity associated with bimetallic catalysts will allow for the use of more complex olefins in the future, in hopes of introducing further structural complexity into the polymer. 

Cooperative catalysts for the copolymerization of carbon dioxide and ethylene

248th National Meeting (2014)

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