Macromolecular Rapid Communications, Vol.30, No.20, 1731-1735, 2009
Metal-Free Activation in the Anionic Ring-Opening Polymerization of Cyclopropane Derivatives
The successful activation observed when using (BuP4)-P-t phosphazene base and thiophenol or bisthiols for the anionic ring opening polymerization (ROP) of di-n-propyl cyclopropane-1,1-dicarboxylate is described. Well-defined monofunctional or difunctional polymers with a very narrow molecular weight distribution were obtained through a living process. Quantitative end-capping of the propagating malonate carbanion was accessible by using either an electrophilic reagent such as allyl bromide or a strong acid such as HCl. Kinetics studies demonstrated a much higher reactivity compared to the conventional route using alkali metal thiophenolates.
Keywords:anionic polymerization;cyclopropane;living polymerization;phosphazene;ring-opening polymerization