Olivier Coulembier

The recent advances in polymerization of lactide (LA) from organic salts enriched the toolbox to prepare well‐defined materials. Herein we report the use of crown ether (CE) as an additive to polymerize the L‐LA when initiated by 12‐hydroxydodecanoic acid (HDA) activated by one equivalent of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU). While both size and structure of the ether additive play an important role on the overall rate of reaction, the CE decomplexation is crucial to outpace transfer reactions and also permit the process to be moderately conducted under air atmosphere by an efficient water trapping process.