Reversible hierarchical structure induced by solvation and temperature modulation in an ionic liquid-based random bottlebrush copolymer

Magurudeniya, Harsha D.; Ringstrand, Bryan S.; Seifert, Sönke; Firestone, Millicent A.

doi:10.1039/C8PY01218K

Title: Reversible hierarchical structure induced by solvation and temperature modulation in an ionic liquid-based random bottlebrush copolymer

Journal Article · Thu Sep 06 00:00:00 EDT 2018 · Polymer Chemistry

DOI:https://doi.org/10.1039/C8PY01218K· OSTI ID:1508373

Magurudeniya, Harsha D. ^[1];

^[1]; Seifert, Sönke ^[2];

^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)

Here a solvent and temperature responsive random copolymer having a polyacrylate backbone with emanating ionic liquid side chains of 1-decyl-3-methylimidazolium chloride and 1-(2-carboxyethyl)-3-imidazolium bromide grafted poly-N-isopropylacrylamide (PNIPAM) possessing bottlebrush architecture is synthesized. The bottlebrush copolymer is prepared using an uncommon route that exploits the co-assembly of two amphiphilic ionic liquid acryloyl-based monomers in 30% (w/w) water to form a lyotropic mesophase followed by photo-initiated free radical polymerization. The copolymer adopts a temperature-invariant 2D hexagonal structure as determined by SAXS in the dehydrated (de-swollen) state. The absence of thermoresponsivity is attributed to a combination of confinement coupled with insufficient solvation of the grafted PNIPAM chains. In a water-swollen state (hydrogel), loss in long range translational ordering is observed while short range temperature-dependent ordering dominates. Below the LCST of PNIPAM (<40 °C), disassociated nanoscale discoidal assemblies predominate, as determined by SAXS. At temperatures above the LCST, the particles condense to form thicker circular discs of similar diameter. Polarized optical microscopy shows the formation of 1-D liquid-crystalline fibrillar structures spanning the meso- to micro-length scales. The assembly and disassembly are fully reversible with temperature cycling. Finally, this work demonstrates the possibility of achieving self-organization over multiple length scales (panoscopic) to create complex structures from modular components using an external stimulus to control construction.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC02-06CH11357; AC52-06NA25396

OSTI ID:: 1508373

Alternate ID(s):: OSTI ID: 1482012

Report Number(s):: LA-UR-18-28367; PCOHC2; 151484

Journal Information:: Polymer Chemistry, Vol. 9, Issue 42; ISSN 1759-9954

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 4 works

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