TY - JOUR
T1 - Modifying Frank-Kasper Mesophases by Modulating Chain Configuration in PDMS- b-PTFEA Copolymers
AU - Jeon, Seungbae
AU - Jun, Taesuk
AU - Jo, Seungyun
AU - Kim, Kyungkon
AU - Lee, Byeongdu
AU - Lee, Sangwoo
AU - Ryu, Du Yeol
N1 - Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
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.
UR - http://www.scopus.com/inward/record.url?scp=85137900385&partnerID=8YFLogxK
U2 - 10.1021/acs.macromol.2c01146
DO - 10.1021/acs.macromol.2c01146
M3 - Article
AN - SCOPUS:85137900385
SN - 0024-9297
VL - 55
SP - 8049
EP - 8057
JO - Macromolecules
JF - Macromolecules
IS - 18
ER -