The ring-opening copolymerization (ROCOP) of CO2/epoxide is an attractive means to synthesize polyols for use in the production of polyurethanes. Herein, a highly active and selective heterodinuclear magnesium-cobalt catalyst is reported for the ROCOP of CO2/cyclohexene oxide. The heterodinuclear MgCo catalyst was synthesized using a one-pot mixed metal precursor feedstock protocol and characterized by mass spectrometry, X-ray photoelectron spectroscopy, super conducting quantum interference device magnetic measurements and cyclic voltammetry. Perfectly alternating copolymer was afforded at 1 bar of CO2 pressure and the catalytic activity is amongst the highest values reported to date showing a turnover frequency of 1200 h-1. Optimization of conditions allows TOFs of over 12000 h-1 without any change to product quality. Kinetic analysis indicated a first order dependence on catalyst and epoxide concentrations and a zero order dependence on CO2 pressure. Eyring analysis shows a lower transition state Gibbs free energy for MgCo versus either the homodinuclear counterparts. Further, the synergy exhibited by MgCo is rationalized in terms of metal specific contributions to transition state entropy and enthalpy values.

Understanding metal synergy in heterodinuclear catalysts for CO2/epoxide 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.