Templated PISA: Driving Polymerization‐Induced Self‐Assembly towards Fibre Morphology

Dispersions of block copolymer fibres in water have many potential applications and can be obtained by polymerization‐induced self‐assembly (PISA), but only under very restricted experimental conditions. In order to enlarge this experimental window, we introduced a supramolecular moiety, a hydrogen‐bonded bis‐urea sticker, in the macromolecular reversible addition fragmentation chain transfer (RAFT) agent to drive the morphology of the nano‐objects produced by RAFT‐mediated PISA towards the fibre morphology. This novel concept is tested in the synthesis of a series of poly(N,N‐dimethylacrylamide)‐b‐poly(2‐methoxyethyl acrylate) (PDMAc‐b‐PMEA) diblock copolymers prepared by dispersion polymerization in water. The results prove that the introduction of the templating bis‐urea stickers into PISA greatly promotes the formation of fibres in a large experimental window.