Abstract
Primary amine functionalized polystyrenes were prepared in quantitative yields by atom transfer radical polymerization using the adduct of 1‐(bromoethyl)benzene with 1‐(4‐aminophenyl)‐1‐phenylethylene as initiator for styrene polymerization in the presence of a copper(I) bromide/N,N,N′,N′,N″‐pentamethyldiethylenetriamine catalyst system. The polymerizations proceeded via a controlled free radical polymerization process to afford quantitative yields of the corresponding primary amine functionalized polystyrenes with predictable molecular weights (M~n~ = 2 × 10^3^ to 10 × 10^3^ g mol^−1^), relatively narrow molecular weight distributions (M~w~/M~n~ = 1.03–1.49), well defined chain‐end functionalities and initiator efficiencies as high as 0.92. The polymerization process was monitored by gas chromatographic analysis. The primary amine functionalized polymers were characterized by thin layer chromatography, size exclusion chromatography, potentiometry and spectroscopy. Experimental results are consistent with quantitative functionalization via the 1,1‐diphenylethylene derivative. Polymerization kinetic measurements show that the polymerization reaction follows first order rate kinetics with respect to monomer consumption and the number average molecular weight increases linearly with monomer conversion.
© 2003 Society of Chemical Industry