| Abstract: | Controlled radical polymerization (CRP) has been experiencing tremendous developments of late, with spectacular achievements in macromolecular engineering. Well‐defined star polymers as well as block copolymers can be obtained using miscellaneous CRP methods. This paper is the second of a series devoted to the synthesis of triblock copolymers by nitroxide‐mediated polymerization, using a β‐hydrogen containing phosphonylated nitroxide (SG1) as stable radical. It focuses on the problems associated with the sequential polymerization of styrene and n‐butyl acrylate while synthesizing poly(styrene‐b‐n‐butyl acrylate‐b‐styrene) copolymers from SG1‐based macromolecular alkoxyamines. In particular, it discloses how the blocking efficiency can be improved when growing the second poly(n‐butyl acrylate) (PBuA) block from the first polystyrene (PS) block. The proportion of dead chains that contaminate such triblock samples is also evaluated. |
