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

The first example of living radical polymerization of vinyl chloride carried out in water at 25 degreesC is reported. This polymerization was initiated by iodoform and catalyzed by nascent Cu-0 produced by the disproportionation of Cu-I in the presence of strongly Cu-II 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 similar toCHC(II) 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 Cu-0 and degenerative chain transfer. (C) 2003 Wiley Periodicals, Inc.