Summary: The polymerizable nitroxide 4‐acryloyloxy‐2,2,6,6‐tetramethylpiperidine‐N‐oxyl (AOTEMPO) was utilized in a two step polymerization to prepare alkoxyamine‐functionalized backbone polymers. These backbones were then used as initiators for stable free‐radical graft polymerizations in bulk at 125 °C. The products were cleaved into their linear components by reaction with L ‐(+)‐ascorbic acid allowing a reproducible analysis of the molecular weights. The influences of the backbone concentration and the graft density on the polymerization were investigated. Graft polymers purely consisting of styrene were produced as well as polymers with a backbone based on 2‐ethoxyethyl acrylate (EOEA). In addition a graft polymer with block copolymer side chains was prepared by extending a preformed graft polymer. In all cases the controlled course of the reaction was confirmed by the linear increase of the molecular weights over conversion and the low polydispersities of the products.
