Living radical polymerization of vinyl chloride initiated with iodoform and catalyzed by nascent Cu0/tris(2‐aminoethyl)amine or polyethyleneimine in water at 25 °C proceeds by a new competing pathways mechanism

Abstract

AbstractThe first example of living radical polymerization of vinyl chloride carried out in water at 25 °C is reported. This polymerization was initiated by iodoform and catalyzed by nascent Cu0 produced by the disproportionation of CuI in the presence of strongly CuII binding ligands such as tris(2‐aminoethyl)amine or polyethyleneimine. The resulting poly(vinyl chloride) was free of structural defects, had controlled molecular weight and narrow molecular weight distribution, contained two ∼CHClI active chain ends, and had a higher syndiotacticity (62%) than the one obtained by conventional free‐radical polymerization at the same temperature (56%). This novel polymerization proceeds, most probably, by a combination of competitive pathways that involves activation by single electron transfer mediated by nascent Cu0 and degenerative chain transfer. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3283–3299, 2003