Silane radicals were used to abstract bromine termini from monobrominated polystyrene (PStBr) in the presence of excess monomer and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), generating polymer radicals that underwent chain extension. Typically, 70-85% of the PStBr precursors were activated by silane radical atom abstraction (SRAA) and were elongated by nitroxide mediated polymerization (NMP), shifting to higher number-average molecular weight (M-n) values as observed by gel permeation chromatography (GPC). Chain extension did not occur until the temperature was elevated to 130 degrees C, with no increase in Mn values observed when the reaction was held at 80 degrees C, which is the temperature of the SRAA phase. The NMP phase of the reaction showed a linear correlation between Mn values and monomer consumption, along with first order kinetics with respect to styrene. SRAA/NMP was then applied to the synthesis of polystyrene-b-poly(n-butyl acrylate) and polystyrene-b-poly(p-methyl styrene), with analysis by GPC indicating the formation of block copolymers with a similar amount of unreacted PStBr remaining. Quantitative activation and elongation of the polymer precursors were prevented due to the ability of both the t-butoxy radicals and tris(trimethylsilyl)silane radicals to add across monomeric double bonds, competing with atom abstraction. Reactions were thus performed in which the monomer was added only after the transition to the higher temperature, which resulted in improved activation of the PStBr. (c) 2008 Elsevier Ltd. All rights reserved.