Polymerisation‐Induced Self‐Assembly of Graft Copolymers

We report the polymerisation‐induced self‐assembly of poly(lauryl methacrylate)‐graft‐poly(benzyl methacrylate) copolymers during reversible addition‐fragmentation chain transfer (RAFT) grafting from polymerisation in a backbone‐selective solvent. Electron microscopy images suggest the phase separat...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2022-11, Vol.61 (44), p.e202210518-n/a
Main Authors: Häkkinen, Satu, Tanaka, Joji, Garcia Maset, Ramón, Hall, Stephen C. L., Huband, Steven, Rho, Julia Y., Song, Qiao, Perrier, Sébastien
Format: Article
Language:English
Subjects:
Assembly
Chain branching
Chain transfer
Copolymers
Electron microscopy
Graft Copolymer
Graft copolymers
Material properties
Micelles
Morphology
Phase separation
PISA
Polymerization
Polymers
RAFT
Self-Assembly
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Summary:We report the polymerisation‐induced self‐assembly of poly(lauryl methacrylate)‐graft‐poly(benzyl methacrylate) copolymers during reversible addition‐fragmentation chain transfer (RAFT) grafting from polymerisation in a backbone‐selective solvent. Electron microscopy images suggest the phase separation of grafts to result in a network of spherical particles, due to the ability of the branched architecture to freeze chain entanglements and to bridge core domains. Small‐angle X‐ray scattering data suggest the architecture promotes the formation of multicore micelles, the core morphology of which transitions from spheres to worms, vesicles, and inverted micelles with increasing volume fraction of the grafts. A time‐resolved SAXS study is presented to illustrate the formation of the inverted phase during a polymerisation. The grafted architecture gives access to unusual morphologies and provides exciting new handles for controlling the polymer structure and material properties. The influence of branching on polymer self‐assembly is investigated by conducting polymerisation‐induced self‐assembly of sparsely grafted poly(lauryl methacrylate)‐graft‐poly(benzyl methacrylate) in n‐dodecane. Electron microscopy and X‐ray scattering techniques are used to characterise the resulting materials.
ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.202210518