Reversible Complexation Mediated Living Radical Polymerization Using Tetraalkylammonium Chloride Catalysts

Abstract This work reports the first use of organic chloride salts as catalysts for reversible complexation mediated living radical polymerization. Owing to the strong halogen‐bond forming ability of Cl − , the studied four tetraalkylammonium chloride catalysts (R 4 N + Cl − ) successfully control the polymerizations of methyl methacrylate, yielding polymers with low dispersities up to high monomer conversion (>90%). Benzyldodecyldimethylammonium chloride is further exploited to other methacrylates and yields low‐dispersity block copolymers. The advantages of the chloride salt catalysts are wide monomer scope, good livingness, accessibility to block copolymers, and good solubility in organic media. Because of the good solubility, the use of the chloride salt catalysts can prevent agglomeration of catalysts on reactor walls in organic media, which is an industrially attractive feature. Among halide anions, chloride anion is the most abundant and least expensive halide anion, and therefore, the use of the chloride salt catalysts may lower the cost of the polymerization.