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

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Abstract

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 (SBCC), 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 fPIL = 0.31 and 0.55. Variation of the alkyl group appeared to influence the strength of the Flory-like interaction parameter of the system, χPS/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.

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

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Publication details

The article was received on 01 Oct 2018, accepted on 21 Dec 2018 and first published on 11 Jan 2019


Article type: Paper
DOI: 10.1039/C8PY01414K
Citation: Polym. Chem., 2019, Advance Article
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    Self-assembly of highly asymmetric, poly(ionic liquid)-rich diblock copolymers and the effects of simple structural modification on phase behaviour

    A. W. May, Z. Shi, D. B. Wijayasekara, D. L. Gin and T. S. Bailey, Polym. Chem., 2019, Advance Article , DOI: 10.1039/C8PY01414K

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