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Sub-3-Nanometer Domain Spacings of Ultrahigh-χ Multiblock Copolymers with Pendant Ionic Groups

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2021

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Park, Jinseok
Winey, Karen I

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ACS nano. ACS Publications. 2021, 15(10), pp. 16738-16747. ISSN 1936-0851. eISSN 1936-086X. Available under: doi: 10.1021/acsnano.1c06734

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We investigated the temperature-dependent phase behavior and interaction parameter of polyethylene-based multiblock copolymers with pendant ionic groups. These step-growth polymers contain short polyester blocks with a single Li+SO3- group strictly alternating with polyethylene blocks of x-carbons (PESxLi, x = 12, 18, 23). At room temperature, these polymers exhibit layered morphologies with semicrystalline polyethylene blocks. Upon heating above the melting point (∼130 °C), PES18Li shows two order-to-order transitions involving Ia3̅d gyroid and hexagonal morphologies. For PES12Li, an order-to-disorder transition accompanies the melting of the polyethylene blocks. Notably, a Flory-Huggins interaction parameter was determined from the disordered morphologies of PES12Li using mean-field theory: χ(T) = 77.4/T + 2.95 (T in Kelvin) and χ(25 °C) ≈ 3.21. This ultrahigh χ indicates that the polar ionic and nonpolar polyethylene segments are highly incompatible and affords well-ordered morphologies even when the combined length of the alternating blocks is just 18-29 backbone atoms. This combination of ultrahigh χ and short multiblocks produces sub-3-nm domain spacings that facilitate the control of block copolymer self-assembly for various fields of study, including nanopatterning.

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540 Chemie

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multiblock copolymer, high-χ block copolymer, ion-containing polymer, self-assembly, phase diagram, nanopatterning

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ISO 690PARK, Jinseok, Anne SAUMER, Stefan MECKING, Karen I WINEY, 2021. Sub-3-Nanometer Domain Spacings of Ultrahigh-χ Multiblock Copolymers with Pendant Ionic Groups. In: ACS nano. ACS Publications. 2021, 15(10), pp. 16738-16747. ISSN 1936-0851. eISSN 1936-086X. Available under: doi: 10.1021/acsnano.1c06734
BibTex
@article{Park2021-10-26Sub3N-55647,
  year={2021},
  doi={10.1021/acsnano.1c06734},
  title={Sub-3-Nanometer Domain Spacings of Ultrahigh-χ Multiblock Copolymers with Pendant Ionic Groups},
  number={10},
  volume={15},
  issn={1936-0851},
  journal={ACS nano},
  pages={16738--16747},
  author={Park, Jinseok and Saumer, Anne and Mecking, Stefan and Winey, Karen I}
}
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