Unimer Exchange Is not Necessary for Morphological Transitions in Polymerization-Induced Self-Assembly |
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Authors: | Clément Debrie Noémie Coudert Dr. Jean-Michel Guigner Dr. Taco Nicolai Dr. François Stoffelbach Dr. Olivier Colombani Dr. Jutta Rieger |
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Affiliation: | 1. Sorbonne Université & CNRS (UMR 8232), Institut Parisien de Chimie Moléculaire (IPCM), Polymer Chemistry Team, 4 Place Jussieu, 75252 Paris Cedex 05, France;2. Le Mans Université & CNRS (UMR 6283), Institut des Molécules et Matériaux du Mans (IMMM), Avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France;3. Sorbonne Université &CNRS, Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie (IMPMC), UMR 7590-IRD-MNHN, 75252 Paris Cedex 05, France |
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Abstract: | Polymerization-induced self-assembly (PISA) has established itself as a powerful and straightforward method to produce polymeric nano-objects of various morphologies in (aqueous) solution. Generally, spheres are formed in the early stages of polymerization that may evolve to higher order morphologies (worms or vesicles), as the solvophobic block grows during polymerization. Hitherto, the mechanisms involved in these morphological transitions during PISA are still not well understood. Combining a systematic study of a representative PISA system with rheological measurements, we demonstrate that—unexpectedly—unimer exchange is not necessary to form higher order morphologies during radical RAFT-mediated PISA. Instead, in the investigated aqueous PISA, the monomer present in the polymerization medium is responsible for the morphological transitions, even though it slows down unimer exchange. |
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Keywords: | Block Copolymers Micelles PISA Rheology Vesicles |
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