Sulfolane as Common Rate Accelerating Solvent for the Cationic Ring-Opening Polymerization of 2-Oxazolines

Abstract

The search for alternative solvents for the cationic ring-opening polymerization (CROP) of 2-methyl-2-oxazoline (MeOx) is driven by the poor solubility of P(MeOx) in polymerization solvents such as acetonitrile (CH₃CN) and chlorobenzene as well as in MeOx itself. In this study, solvent screening has revealed that especially sulfolane is a good solvent for PMeOx. Unexpectedly, an increased propagation rate constant (<i>k</i>_p) was found for the CROP of MeOx in sulfolane. Further extended kinetic studies at different temperatures (60-180 °C), revealed that the acceleration is due to an increase in frequency factor, while the activation energy (<i>E</i>_a) of the reaction is hardly affected. In order to explore the versatility of sulfolane as polymerization solvent for the CROP of 2-oxazolines in general, also the polymerization kinetics of other 2-oxazoline monomers, such as 2-ethyl-2-oxazoline (EtOx) and 2-phenyl-2-oxazoline (PhOx), have been studied, revealing a common acceleration of the CROP of 2-oxazoline monomers in sulfolane. This also enabled more controlled synthesis of PMeOx-<i>block</i>-PPhOx block copolymers that otherwise suffers from solvent incompatibility.