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.