Self-assembly of highly asymmetric, poly(ionic liquid)-rich diblock copolymers and the effects of simple structural modification on phase behaviour

May, Alyssa W.; Shi, Zhangxing; Wijayasekara, Dilanji B.; Gin, Douglas L.; Bailey, Travis S.

doi:10.1039/c8py01414k

Title: Self-assembly of highly asymmetric, poly(ionic liquid)-rich diblock copolymers and the effects of simple structural modification on phase behaviour

Journal Article · Fri Jan 11 00:00:00 EST 2019 · Polymer Chemistry

DOI:https://doi.org/10.1039/c8py01414k· OSTI ID:1613571

^[1]; Shi, Zhangxing ^[2]; Wijayasekara, Dilanji B. ^[1];

^[2];

^[1]

Colorado State Univ., Fort Collins, CO (United States)
Univ. of Colorado, Boulder, CO (United States)

A series of thermally processable, phase-separating diblock copolymers made via sequential ATRP of styrene and styrenic ionic liquid (IL) monomers with various alkyl imidazolium substituents were synthesized to cover a wide range of volume fractions, most notably those on the IL-rich side of the phase diagram. Small-angle X-ray scattering (SAXS) analysis was used to confirm melt-state (and glassy state) phase behavior in which all four classic equilibrium diblock copolymer morphologies – body-centered cubic spheres (S_BCC), hexagonally packed cylinders (Hex), lamellae (Lam), and notably, bicontinuous gyroid (Gyr) – were observed. These PS-PIL diblock copolymers were found to have a high degree of conformational asymmetry and/or electrostatic cohesion within the PIL block, highlighted by the shift of the Lam phase window with boundaries falling between f_PIL = 0.31 and 0.55. Finally, variation of the alkyl group appeared to influence the strength of the Flory-like interaction parameter of the system, χ_PS/PIL, such that simple substitution of methyl by n-butyl on the imidazolium IL substituent resulted in the emergence of the (notoriously segregation-sensitive) Gyr phase, superseding the persistent coexistence of Lam and Hex in the methyl-substituted imidazolium diblock copolymer phase diagram.

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Research Organization:: Arizona State Univ., Tempe, AZ (United States); Univ. of Colorado, Boulder, CO (United States)

Sponsoring Organization:: USDOE Advanced Research Projects Agency - Energy (ARPA-E); National Science Foundation (NSF)

Grant/Contract Number:: AR0000343; AR0000770; CBET-1160026; DMR-1808824; DMR-0821799

OSTI ID:: 1613571

Alternate ID(s):: OSTI ID: 1490548

Journal Information:: Polymer Chemistry, Vol. 10, Issue 6; ISSN 1759-9954

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 7 works

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