Modifying Frank-Kasper Mesophases by Modulating Chain Configuration in PDMS- b-PTFEA Copolymers

Seungbae Jeon; Taesuk Jun; Seungyun Jo; Kyungkon Kim; Byeongdu Lee; Sangwoo Lee; Du Yeol Ryu

doi:10.1021/acs.macromol.2c01146

Modifying Frank-Kasper Mesophases by Modulating Chain Configuration in PDMS- b-PTFEA Copolymers

Seungbae Jeon, Taesuk Jun, Seungyun Jo, Kyungkon Kim, Byeongdu Lee, Sangwoo Lee, Du Yeol Ryu

Department of Chemical and Biomolecular Engineering

Research output: Contribution to journal › Article › peer-review

1 Citation (Scopus)

Abstract

The common spherical mesophases observed from chemically distinct compounds have promoted extensive studies of packing structures in soft-matter self-assemblies. Here, we present a new approach for controlling sphere-packing phases by modulating homologous copolymer chain configurations. To this end, three sets of sample pairs, compositionally asymmetric polydimethylsiloxane-b-poly(2,2,2-trifluoroethyl acrylate) (PDMS-b-PTFEA) diblock copolymers (diBCPs) and their homologues containing the corresponding triblock copolymer (triBCP), are synthesized via atom transfer radical polymerization and designed with the consistent volume fractions of the core-forming PTFEA block, f_PTFEA= 0.20, 0.18, and 0.15. We identify the formation of C15 and hexagonally close-packed (HCP) phases in the triBCP-containing PDMS-b-PTFEAs, whereas the σ and C14 phases are formed in their diBCP analogues, respectively. These phase shifts into C15 and HCP, due to molecular configuration differences, reveal a significant yet unrealized role of chain configurations and the associated chain size effects in determining the stable sphere-packing phases in BCP systems.

Original language	English
Pages (from-to)	8049-8057
Number of pages	9
Journal	Macromolecules
Volume	55
Issue number	18
DOIs	https://doi.org/10.1021/acs.macromol.2c01146
Publication status	Published - 2022 Sept 27

Bibliographical note

Funding Information:
This research was supported by the NRF grants (2021R1A2C2006588, 2019M1A2A2072417, and 2022R1A4A1020543) funded by the Ministry of Science, ICT & Future Planning (MSIP), Korea. S. Jeon acknowledges the International Joint Research Grant from Yonsei Graduate School, Korea.

Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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10.1021/acs.macromol.2c01146

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title = "Modifying Frank-Kasper Mesophases by Modulating Chain Configuration in PDMS- b-PTFEA Copolymers",

abstract = "The common spherical mesophases observed from chemically distinct compounds have promoted extensive studies of packing structures in soft-matter self-assemblies. Here, we present a new approach for controlling sphere-packing phases by modulating homologous copolymer chain configurations. To this end, three sets of sample pairs, compositionally asymmetric polydimethylsiloxane-b-poly(2,2,2-trifluoroethyl acrylate) (PDMS-b-PTFEA) diblock copolymers (diBCPs) and their homologues containing the corresponding triblock copolymer (triBCP), are synthesized via atom transfer radical polymerization and designed with the consistent volume fractions of the core-forming PTFEA block, fPTFEA= 0.20, 0.18, and 0.15. We identify the formation of C15 and hexagonally close-packed (HCP) phases in the triBCP-containing PDMS-b-PTFEAs, whereas the σ and C14 phases are formed in their diBCP analogues, respectively. These phase shifts into C15 and HCP, due to molecular configuration differences, reveal a significant yet unrealized role of chain configurations and the associated chain size effects in determining the stable sphere-packing phases in BCP systems.",

author = "Seungbae Jeon and Taesuk Jun and Seungyun Jo and Kyungkon Kim and Byeongdu Lee and Sangwoo Lee and Ryu, {Du Yeol}",

note = "Funding Information: This research was supported by the NRF grants (2021R1A2C2006588, 2019M1A2A2072417, and 2022R1A4A1020543) funded by the Ministry of Science, ICT & Future Planning (MSIP), Korea. S. Jeon acknowledges the International Joint Research Grant from Yonsei Graduate School, Korea. Publisher Copyright: {\textcopyright} 2022 American Chemical Society. All rights reserved.",

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AU - Lee, Byeongdu

AU - Lee, Sangwoo

AU - Ryu, Du Yeol

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PY - 2022/9/27

Y1 - 2022/9/27

N2 - The common spherical mesophases observed from chemically distinct compounds have promoted extensive studies of packing structures in soft-matter self-assemblies. Here, we present a new approach for controlling sphere-packing phases by modulating homologous copolymer chain configurations. To this end, three sets of sample pairs, compositionally asymmetric polydimethylsiloxane-b-poly(2,2,2-trifluoroethyl acrylate) (PDMS-b-PTFEA) diblock copolymers (diBCPs) and their homologues containing the corresponding triblock copolymer (triBCP), are synthesized via atom transfer radical polymerization and designed with the consistent volume fractions of the core-forming PTFEA block, fPTFEA= 0.20, 0.18, and 0.15. We identify the formation of C15 and hexagonally close-packed (HCP) phases in the triBCP-containing PDMS-b-PTFEAs, whereas the σ and C14 phases are formed in their diBCP analogues, respectively. These phase shifts into C15 and HCP, due to molecular configuration differences, reveal a significant yet unrealized role of chain configurations and the associated chain size effects in determining the stable sphere-packing phases in BCP systems.

AB - The common spherical mesophases observed from chemically distinct compounds have promoted extensive studies of packing structures in soft-matter self-assemblies. Here, we present a new approach for controlling sphere-packing phases by modulating homologous copolymer chain configurations. To this end, three sets of sample pairs, compositionally asymmetric polydimethylsiloxane-b-poly(2,2,2-trifluoroethyl acrylate) (PDMS-b-PTFEA) diblock copolymers (diBCPs) and their homologues containing the corresponding triblock copolymer (triBCP), are synthesized via atom transfer radical polymerization and designed with the consistent volume fractions of the core-forming PTFEA block, fPTFEA= 0.20, 0.18, and 0.15. We identify the formation of C15 and hexagonally close-packed (HCP) phases in the triBCP-containing PDMS-b-PTFEAs, whereas the σ and C14 phases are formed in their diBCP analogues, respectively. These phase shifts into C15 and HCP, due to molecular configuration differences, reveal a significant yet unrealized role of chain configurations and the associated chain size effects in determining the stable sphere-packing phases in BCP systems.

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Modifying Frank-Kasper Mesophases by Modulating Chain Configuration in PDMS- b-PTFEA Copolymers

Abstract

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