Living radical polymerization via organic superbase catalysis

Organic superbases reacted with alkyl iodides (R-I) to reversibly generate the corresponding alkyl radicals (R^•). Via this reaction, organic superbases were utilized as new and highly efficient organic catalysts in living radical polymerization. The superbase catalysts included guanidines, aminophosphines and phosphazenes. Low-polydispersity polymers (M_w/M_n = 1.1-1.4) were obtained up to high conversions (e.g., 80%) in reasonably short times (3-12 h) at mild temperatures (60-80 °C) for methyl methacrylate, styrene and several functional methacrylates. The high polymerization rate and good monomer versatility are attractive features of these superbase catalysts.