Complex and hierarchical micelle architectures from diblock copolymers using living, crystallization-driven polymerizations

• Published in: Nature materials Vol. 8; no. 2; pp. 144 - 150
• Main Authors: Winnik, Mitchell A, Manners, Ian, Gädt, Torben, Ieong, Nga Sze, Cambridge, Graeme
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 01.02.2009; Nature Publishing Group
• Subjects: Biomaterials; Blood Platelets - chemistry; Chemical engineering; Chemistry and Materials Science; Condensed Matter Physics; Crystallization; Fabrication; Materials Science; Micelles; Microscopy, Atomic Force; Microscopy, Electron, Transmission; Nanotechnology; Optical and Electronic Materials; Polymers; Polymers - chemistry; Solvents
• ISSN: 1476-1122; 1476-4660
• DOI: 10.1038/nmat2356

Block copolymers consist of two or more chemically distinct polymer segments, or blocks, connected by a covalent link. In a selective solvent for one of the blocks, core–corona micelle structures are formed. We demonstrate that living polymerizations driven by the epitaxial crystallization of a core-forming metalloblock represent a synthetic tool that can be used to generate complex and hierarchical micelle architectures from diblock copolymers. The use of platelet micelles as initiators enables the formation of scarf-like architectures in which cylindrical micelle tassels of controlled length are grown from specific crystal faces. A similar process enables the fabrication of brushes of cylindrical micelles on a crystalline homopolymer substrate. Living polymerizations driven by heteroepitaxial growth can also be accomplished and are illustrated by the formation of tri- and pentablock and scarf architectures with cylinder–cylinder and platelet–cylinder connections, respectively, that involve different core-forming metalloblocks. A synthetic tool that uses living polymerizations driven by epitaxial crystallization is shown to create a range of complex micelle architectures made from diblock copolymers. Platelet micelles act as initiators for the formation of scarf-like structures with micellar tassels of controlled length, grown from specific locations.