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Synthesis of Block Copolymer Brush by RAFT and Click Chemistry and Its Self-Assembly as a Thin Film
Open AccessArticle

Precise Synthesis and Thin Film Self-Assembly of PLLA-b-PS Bottlebrush Block Copolymers

Laboratoire de Chimie des Polymères Organiques, Université de Bordeaux, CNRS, Bordeaux INP, LCPO, UMR 5629, F-33600 Pessac, France
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Author to whom correspondence should be addressed.
Academic Editor: Irrea Alessia
Molecules 2021, 26(5), 1412; https://doi.org/10.3390/molecules26051412
Received: 16 February 2021 / Revised: 26 February 2021 / Accepted: 3 March 2021 / Published: 5 March 2021
(This article belongs to the Special Issue Copolymers: Preparation and Applications)
The ability of bottlebrush block copolymers (BBCPs) to self-assemble into ordered large periodic structures could greatly expand the scope of photonic and membrane technologies. In this paper, we describe a two-step synthesis of poly(l-lactide)-b-polystyrene (PLLA-b-PS) BBCPs and their rapid thin-film self-assembly. PLLA chains were grown from exo-5-norbornene-2-methanol via ring-opening polymerization (ROP) of l-lactide to produce norbornene-terminated PLLA. Norbonene-terminated PS was prepared using anionic polymerization followed by a termination reaction with exo-5-norbornene-2-carbonyl chloride. PLLA-b-PS BBCPs were prepared from these two norbornenyl macromonomers by a one-pot sequential ring opening metathesis polymerization (ROMP). PLLA-b-PS BBCPs thin-films exhibited cylindrical and lamellar morphologies depending on the relative block volume fractions, with domain sizes of 46–58 nm and periodicities of 70–102 nm. Additionally, nanoporous templates were produced by the selective etching of PLLA blocks from ordered structures. The findings described in this work provide further insight into the controlled synthesis of BBCPs leading to various possible morphologies for applications requiring large periodicities. Moreover, the rapid thin film patterning strategy demonstrated (>5 min) highlights the advantages of using PLLA-b-PS BBCP materials beyond their linear BCP analogues in terms of both dimensions achievable and reduced processing time. View Full-Text
Keywords: bottlebrush block copolymer; sequential ROMP; thin film self-assembly; nanoporous templates bottlebrush block copolymer; sequential ROMP; thin film self-assembly; nanoporous templates
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MDPI and ACS Style

Ji, E.; Cummins, C.; Fleury, G. Precise Synthesis and Thin Film Self-Assembly of PLLA-b-PS Bottlebrush Block Copolymers. Molecules 2021, 26, 1412. https://doi.org/10.3390/molecules26051412

AMA Style

Ji E, Cummins C, Fleury G. Precise Synthesis and Thin Film Self-Assembly of PLLA-b-PS Bottlebrush Block Copolymers. Molecules. 2021; 26(5):1412. https://doi.org/10.3390/molecules26051412

Chicago/Turabian Style

Ji, Eunkyung; Cummins, Cian; Fleury, Guillaume. 2021. "Precise Synthesis and Thin Film Self-Assembly of PLLA-b-PS Bottlebrush Block Copolymers" Molecules 26, no. 5: 1412. https://doi.org/10.3390/molecules26051412

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