Block Copolymers of Poly(2-oxazoline)s and Poly(meth)acrylates: A Crossover between Cationic Ring-Opening Polymerization (CROP) and Reversible Addition–Fragmentation Chain Transfer (RAFT)

To combine the advantages of poly(2-oxazoline)s (POx) and controlled radical polymerization (CRP) techniques, the cationic ring-opening polymerization (CROP) of 2-methyl-2-oxazoline (MeOx), 2-ethyl-2-oxazoline (EtOx), and 2-<i>n</i>-nonyl-2-oxazoline (NonOx) were terminated with a carboxylic acid functionalized chain transfer agent (CTA). The obtained PEtOx with a high degree of functionalization (DF) was used as macro-CTA for the reversible addition-fragmentation chain transfer (RAFT) polymerization of various vinylic monomers (styrene (St), methyl acrylate (MA), <i>tert</i>-butyl acrylate (<i>t</i>BuA), acrylic acid (AA), <i>N</i>,<i>N</i>-dimethyl acrylamide (DMAAm), and <i>N</i>,<i>N</i>-dimethylaminoethylacrylate (DMAEA)) resulting in well-defined block copolymers. Thus, in this work we report a versatile route to combine poly(2-oxazoline)s prepared via CROP with RAFT polymerization for the synthesis of novel block copolymers.