The Effect of Hydrophile Topology in RAFT-Mediated Polymerization-Induced Self-Assembly

Polymerization‐induced self‐assembly (PISA) was employed to compare the self‐assembly of different amphiphilic block copolymers. They were obtained by emulsion polymerization of styrene in water using hydrophilic poly(N‐acryloylmorpholine) (PNAM)‐based macromolecular RAFT agents with different struc...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2016-03, Vol.55 (11), p.3739-3743
Main Authors: Lesage de la Haye, Jennifer, Zhang, Xuewei, Chaduc, Isabelle, Brunel, Fabrice, Lansalot, Muriel, D'Agosto, Franck
Format: Article
Language:English
Subjects:
amphiphiles
Backbone
Block copolymers
Chains (polymeric)
Chemical Sciences
Copolymers
Emulsion polymerization
Ethylene glycol
Hydrophobicity
Macromolecules
nanoparticles
Nanostructure
Polyethylene glycol
Polymerization
Polystyrene
Polystyrene resins
RAFT polymerization
Self-assembly
Styrene
Topology
Vesicles
water
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Summary:Polymerization‐induced self‐assembly (PISA) was employed to compare the self‐assembly of different amphiphilic block copolymers. They were obtained by emulsion polymerization of styrene in water using hydrophilic poly(N‐acryloylmorpholine) (PNAM)‐based macromolecular RAFT agents with different structures. An average of three poly (ethylene glycol acrylate) (PEGA) units were introduced either at the beginning, statistically, or at the end of a PNAM backbone, resulting in formation of nanometric vesicles and spheres from the two former macroRAFT architectures, and large vesicles from the latter. Compared to the spheres obtained with a pure PNAM macroRAFT agent, composite macroRAFT architectures promoted a dramatic morphological change. The change was induced by the presence of PEGA hydrophilic side‐chains close to the hydrophobic polystyrene segment. An average of three PEGA units were introduced either at the beginning, statistically, or at the end of a hydrophilic segment, resulting in formation of various block copolymer morphologies. Key: a) Same hydrophilic comonomers; b) various hydrophilic macroRAFTs; c) different particle morphologies (spheres, nanovesicles, large vesicles), N‐acryloyl morpholine (• (blue)), PEG acrylate (•••• (green)).
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201511159