Hierarchically structured assemblies of poly(ionic liquid)s with different morphology, arrangement of ionic liquid groups and response to external stimuli are the critical to energy storage, electrochemistry, catalysis and development of programmable interfaces. In this study, we analyzed the assembly of a new library of amphiphilic poly(ionic liquid)s with linear and hyperbranched architectures based on hydrophobic polyester fragments and peripheral hydrophilic ammonium carboxylates in aqueous media. The novel thermally responsive poly(ionic liquid)s were synthesized by neutralization of terminal carboxyl groups of polycarboxylic acids by amine terminated poly(N-isopropylacrylamide) (PNIPAM) to create temperature-sensitive shells. The low critical solution temperature (LCST) of poly(ionic liquid)s with linear and hyperbranched architecture increased for compounds with greater NIPAM content but is consistently lower than that for linear counterparts. We found that the poly(ionic liquid)s with linear architecture form micellar assemblies with a variety morphologies, such as unimolecular micelles and micelle aggregates at the variation content of outer PNIPAM macrocations. At the same time, hyperbranched poly(ionic liquid)s form smaller micelle aggregates. Moreover, we found network-like or spherical aggregates, vesicles and spherical particles and suggested multi-length scale hierarchical model and corresponding assembly transformations during phase transitions associated with abrupt changes in hydrophobic-hydrophilic balance of thermoresponsive polyionic liquids.

Beyond spherical assemblies of hyperbranched poly(ionic liquid)s

256th National Meeting (2018)

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