Influence of Charge Fraction on the Phase Behavior of Symmetric Single-Ion Conducting Diblock Copolymers

Zhang, Bo; Zheng, Caini; Sims, Michael B.; Bates, Frank S.; Lodge, Timothy P.

doi:10.1021/acsmacrolett.1c00393

Influence of Charge Fraction on the Phase Behavior of Symmetric Single-Ion Conducting Diblock Copolymers

Journal Article · Fri Jul 23 00:00:00 EDT 2021 · ACS Macro Letters

DOI:https://doi.org/10.1021/acsmacrolett.1c00393· OSTI ID:1831774

^[1]; Zheng, Caini ^[2]; ^[2]; ^[2]; ^[2]

Univ. of Minnesota, Minneapolis, MN (United States); University of MInnesota
Univ. of Minnesota, Minneapolis, MN (United States)

A series of symmetric poly[(oligo(ethylene glycol) methyl ether methacrylate-co-oligo(ethylene glycol) propyl sodium sulfonate methacrylate)]-block-polystyrene (PsOEGMA-PS) diblock copolymers were synthesized as a model system to probe the effect of charge fraction on the phase behavior of charged-neutral single-ion conducting diblock copolymers. Small-angle X-ray scattering (SAXS) experiments showed that increasing the charge fraction does not alter the ordered phase morphology (lamellar) but increases the order–disorder transition temperature (T_ODT) significantly. Additionally, the effective Flory–Huggins interaction parameter (χ_eff) was found to increase linearly with the charge fraction, similar to the case of conventional salt-doped diblock copolymers. This indicates that the effect of counterion solvation, attributed to the significant mismatch between the dielectric constant of each block, provides the dominant effect in tuning the phase behavior of this charged diblock copolymer. Lastly, we therefore infer that electrostatic cohesion (local charge ordering induced by Coulombic interactions), which is predicted to suppress microphase separation and lead to asymmetric phase diagrams, only plays a minor role in this model system.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Minnesota, Twin Cities, MN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0017809

OSTI ID:: 1831774

Journal Information:: ACS Macro Letters, Journal Name: ACS Macro Letters Journal Issue: 8 Vol. 10; ISSN 2161-1653

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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