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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 (Mw/Mn = 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

Living Radical Polymerization via Organic Superbase Catalysis