Diblock and triblock copolymers of styrene and acetoxymethylstyrene by one-pot ATRP

We describe the synthesis of diblock and triblock copolymers by sequential atom transfer radical polymn. of styrene and acetoxymethylstyrene. Contrary to the usual block copolymn. involving isolation of the macroinitiator, a convenient one-pot procedure is developed. This is possible because of the preferential polymn. of acetoxymethylstyrene, even in the presence of residual styrene, as inferred from characterization of the intermediate polystyrenes and the block copolymers by size exclusion chromatog., 1H NMR, Fourier transform IR spectroscopy, differential scanning calorimetry, and GPEC techniques. The latent acetoxy functionalities in these block copolymers are shown to be easily unmasked to -OH and -Br functionalities, with the potential for block ionomers and dense graft architectures