N-oxyl controlled free radical solution polymerization of styrene

The radical solution polymerization (solvent: anisole) controlled by 2,2,6, 6-tetramethylpiperidine-N-oxyl (TEMPO) makes possible to synthesize block c opolymers with higher molecular weights, as well as to polymerize solid mon omers. Polystyrene previously terminated by TEMPO was employed as a macroin itiator, which was then polymerized at various styrene/anisole ratios, temp eratures, and initiator concentrations (initiator: dicumyl peroxide). In ad dition, model calculations were employed to study the initiator-based accel eration and to simulate the product composition of the resulting polymer. T he controlled radical polymerizations in solution and in bulk can be perfor med through dosed initiator addition with comparable rates of polymerizatio n.