Multidimensional kinetic study on the organocatalyzed ring-opening polymerization (ROP) of <scp>l</scp> -lactide <i>via</i> a robotic high-throughput flow platform

Ring-opening polymerization (ROP) of l-lactide catalyzed by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) was efficiently screened <i>via</i> a programmable high-throughput robotic flow platform with very high accuracy (absolute error <5%). With a very significant amount of data being generated, a rate law describing living ROP initiated by TBD that includes a first-order dependency in l-lactide, a first-order dependency in TBD and a half-order dependency in the initiator 4-methylbenzyl alcohol is developed. Additionally, a negative observed reaction rate (<i>k</i> _obs) was determined with increasing the initial monomer concentration, initiator or catalyst, or, surprisingly, decreasing the reaction temperature, giving rise to negative activation energies within the chemical space studied.