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

Angew Chem Int Ed Engl. 2019 Mar 4;58(10):3173-3177. doi: 10.1002/anie.201809370. Epub 2018 Dec 20.

Abstract

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.

Keywords: block copolymers; hydrogen bonds; nanofibers; self-assembly; supramolecular chemistry.