The combination of controlled polymerization techniques and "click" reactions form an efficient platform for the preparation of polymers in various architectures. In this critical review, an update of our 2007 review in Chem. Soc. Rev., we focus on the "click" reactions that have been used widely in the last four years to create new polymer architectures. Not only block copolymers and star-shaped polymers but also cyclic and dendritic macromolecules could be synthesized using these robust "click" reactions (205 references).

This work describes the polymerization of the free secondary amine bearing monomer 2,2,6,6‐tetramethylpiperidin‐4‐yl methacrylate (TMPMA) by means of different controlled radical polymerization techniques (ATRP, RAFT, NMP). In particular, reversible addition‐fragmentation chain transfer (RAFT) polymerization enabled a good control at high conversions and a polydispersity index below 1.3, thereby enabling the preparation of well‐defined polymers. Remarkably, the polymerization of the secondary amine bearing methacrylate monomer was not hindered by the presence of the free amine that commonly induces degradation of the RAFT reagent. Subsequent oxidation of the polymer yielded the polyradical poly(2,2,6,6‐tetramethylpiperidinyloxy‐4‐yl methacrylate), which represents a valuable material used in catalysis as well as for modern batteries. The obtained polymers having a molar mass (Mn) of 10,000–20,000 g/mol were used to fabricate well‐defined, radical‐bearing polymer films by inkjet‐ printing. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

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-2oxazoline (MeOx), 2-ethyl-2-oxazoline (EtOx), and 2-n-nonyl-2oxazoline (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), tert-butyl acrylate (tBuA), acrylic acid (AA), N,N-dimethyl acrylamide (DMAAm), and N,N-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.