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Small‐Angle X‐Ray Scattering Studies of Block Copolymer Nano‐Objects: Formation of Ordered Phases in Concentrated Solution During Polymerization‐Induced Self‐Assembly

We report that polymerization‐induced self‐assembly (PISA) can be used to prepare lyotropic phases comprising diblock copolymer nano‐objects in non‐polar media. RAFT dispersion polymerization of benzyl methacrylate (BzMA) at 90 °C using a trithiocarbonate‐capped hydrogenated polybutadiene (PhBD) ste...

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Autores principales: Rymaruk, Matthew J., O'Brien, Cate T., György, Csilla, Darmau, Bastien, Jennings, James, Mykhaylyk, Oleksandr O., Armes, Steven P.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8252599/
https://www.ncbi.nlm.nih.gov/pubmed/33725372
http://dx.doi.org/10.1002/anie.202101851
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author Rymaruk, Matthew J.
O'Brien, Cate T.
György, Csilla
Darmau, Bastien
Jennings, James
Mykhaylyk, Oleksandr O.
Armes, Steven P.
author_facet Rymaruk, Matthew J.
O'Brien, Cate T.
György, Csilla
Darmau, Bastien
Jennings, James
Mykhaylyk, Oleksandr O.
Armes, Steven P.
author_sort Rymaruk, Matthew J.
collection PubMed
description We report that polymerization‐induced self‐assembly (PISA) can be used to prepare lyotropic phases comprising diblock copolymer nano‐objects in non‐polar media. RAFT dispersion polymerization of benzyl methacrylate (BzMA) at 90 °C using a trithiocarbonate‐capped hydrogenated polybutadiene (PhBD) steric stabilizer block in n‐dodecane produces either spheres or worms that exhibit long‐range order at 40 % w/w solids. NMR studies enable calculation of instantaneous copolymer compositions for each phase during the BzMA polymerization. As the PBzMA chains grow longer when targeting PhBD(80)–PBzMA(40), time‐resolved small‐angle X‐ray scattering reveals intermediate body‐centered cubic (BCC) and hexagonally close‐packed (HCP) sphere phases prior to formation of a final hexagonal cylinder phase (HEX). The HEX phase is lost on serial dilution and the aligned cylinders eventually form disordered flexible worms. The HEX phase undergoes an order–disorder transition on heating to 150 °C and a pure HCP phase forms on cooling to 20 °C.
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spelling pubmed-82525992021-07-09 Small‐Angle X‐Ray Scattering Studies of Block Copolymer Nano‐Objects: Formation of Ordered Phases in Concentrated Solution During Polymerization‐Induced Self‐Assembly Rymaruk, Matthew J. O'Brien, Cate T. György, Csilla Darmau, Bastien Jennings, James Mykhaylyk, Oleksandr O. Armes, Steven P. Angew Chem Int Ed Engl Research Articles We report that polymerization‐induced self‐assembly (PISA) can be used to prepare lyotropic phases comprising diblock copolymer nano‐objects in non‐polar media. RAFT dispersion polymerization of benzyl methacrylate (BzMA) at 90 °C using a trithiocarbonate‐capped hydrogenated polybutadiene (PhBD) steric stabilizer block in n‐dodecane produces either spheres or worms that exhibit long‐range order at 40 % w/w solids. NMR studies enable calculation of instantaneous copolymer compositions for each phase during the BzMA polymerization. As the PBzMA chains grow longer when targeting PhBD(80)–PBzMA(40), time‐resolved small‐angle X‐ray scattering reveals intermediate body‐centered cubic (BCC) and hexagonally close‐packed (HCP) sphere phases prior to formation of a final hexagonal cylinder phase (HEX). The HEX phase is lost on serial dilution and the aligned cylinders eventually form disordered flexible worms. The HEX phase undergoes an order–disorder transition on heating to 150 °C and a pure HCP phase forms on cooling to 20 °C. John Wiley and Sons Inc. 2021-05-01 2021-06-01 /pmc/articles/PMC8252599/ /pubmed/33725372 http://dx.doi.org/10.1002/anie.202101851 Text en © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Research Articles
Rymaruk, Matthew J.
O'Brien, Cate T.
György, Csilla
Darmau, Bastien
Jennings, James
Mykhaylyk, Oleksandr O.
Armes, Steven P.
Small‐Angle X‐Ray Scattering Studies of Block Copolymer Nano‐Objects: Formation of Ordered Phases in Concentrated Solution During Polymerization‐Induced Self‐Assembly
title Small‐Angle X‐Ray Scattering Studies of Block Copolymer Nano‐Objects: Formation of Ordered Phases in Concentrated Solution During Polymerization‐Induced Self‐Assembly
title_full Small‐Angle X‐Ray Scattering Studies of Block Copolymer Nano‐Objects: Formation of Ordered Phases in Concentrated Solution During Polymerization‐Induced Self‐Assembly
title_fullStr Small‐Angle X‐Ray Scattering Studies of Block Copolymer Nano‐Objects: Formation of Ordered Phases in Concentrated Solution During Polymerization‐Induced Self‐Assembly
title_full_unstemmed Small‐Angle X‐Ray Scattering Studies of Block Copolymer Nano‐Objects: Formation of Ordered Phases in Concentrated Solution During Polymerization‐Induced Self‐Assembly
title_short Small‐Angle X‐Ray Scattering Studies of Block Copolymer Nano‐Objects: Formation of Ordered Phases in Concentrated Solution During Polymerization‐Induced Self‐Assembly
title_sort small‐angle x‐ray scattering studies of block copolymer nano‐objects: formation of ordered phases in concentrated solution during polymerization‐induced self‐assembly
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8252599/
https://www.ncbi.nlm.nih.gov/pubmed/33725372
http://dx.doi.org/10.1002/anie.202101851
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