The direct synthesis of methacrylic-based soft polymeric nanoparticles via reversible addition-fragmentation chain transfer dispersion polymerization (RAFTDP) is described. The use of poly[2-(dimethylamino)ethyl methacrylate]s, of varying average degree of polymerization (X¯n), as the stabilizing blocks for the RAFTDP of 3-phenylpropyl methacrylate (PPMA) in ethanol at 70 °C, at various total solids contents, yielded the full spectrum of self-assembled nanoparticles (spherical and worm aggregates and polymersomes). We also demonstrate that nanoparticle morphology can be tuned simply by controlling temperature. This is especially evident in the case of worm aggregates undergoing a thermoreversible transition to spherical species - a process that is accompanied by a macroscopic degelation-gelation process.

The radical thiol‐ene reaction is used to modify the backbone of a common ROMP‐prepared homopolymer. Hydrothiolation is successful in most instances in facilitating the ready introduction of a range of functionality including OH, pyrrole, alkyl, ester, and POSS species while still retaining the well‐defined characteristics of the parent polymer.

The aim of this article is to highlight recent examples in which two powerful synthetic tools, namely ring-opening metathesis polymerization (ROMP) and thiol-ene (including the thiol-Michael variant) click chemistry have been combined to facilitate the preparation of novel functional materials of varying topology.