The synthesis of poly(lactic acid), PLA, is facile in the presence of the cyclic, organic amidine catalyst 1,8-diazabicyclo[5.4.0]undec-7-ene, DBU. Since DBU’s catalytic capability was first reported by Lohmeijer and colleagues in 2006 for ring-opening polymerizations (ROP), there have been numerous studies conducted by a variety of groups on the catalytic functioning of DBU in the ROPs of cyclic esters resulting in a large body of un-unified material from a mechanistic standpoint. This lack of clarity will hamper engineering polymers with desired characteristics from cyclic ester and lactone monomers. The work outlined in this paper seeks to propose a unified picture of the mechanisms in the DBU catalyzed ROP of lactide. In providing this unified picture of the ROP our work encompassed: (i) proposing a detailed reaction network scheme, (ii) conducting syntheses of lactide and DBU over a range of initial concentrations, and (iii) kinetic modeling to further support the proposed reaction network. As a result, our work has produced: (i) kinetic data, (ii) a consistent, viable reaction scheme verified through kinetic modeling, (iii) deduced and quantified the interplay between polymerization routes facilitated by the presence of DBU, thus demonstrating the need for detailed kinetic studies to deconstruct complex reaction networks, (iv) the first experimental evidence in support of the combination of ketene aminal-ended chains with alcohol-ended chains, and (v) analyzed the robustness of the catalyst to acid contamination.
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