Ionic liquid mixed with poly(methyl methacrylate)-grafted nanoparticle aggregates at low particle concentrations was shown to exhibit different dynamics and ionic conductivity than that of pure ionic liquid in our previous studies. In this work, we report on the quasi-elastic neutron scattering results on ionic liquid containing polymer-grafted nanoparticles at the higher particle concentration. The diffusivity of imidazolium (HMIM + ) cations of 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HMIM-TFSI) in the presence of poly(methyl methacrylate)-grafted iron oxide nanoparticles and the ionic conductivity of solutions were discussed through the confinement. Analysis of the elastic incoherent structure factor suggested the confinement radius decreased with the addition of grafted particles in HMIM-TFSI/solvent mixture, indicating the confinement that is induced by the high concentration of grafted particles, shrinks the HMIM-TFSI restricted volume. We further conjecture that this enhanced diffusivity occurs as a result of the local ordering of cations within aggregates of poly(methyl methacrylate)-grafted particles.
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Unusual Lower Critical Solution Temperature Phase Behavior of Poly(benzyl methacrylate) in a Pyrrolidinium-Based Ionic Liquid
Polymer/ionic liquid systems are being increasingly explored, yet those exhibiting lower critical solution temperature (LCST) phase behavior remain poorly understood. Poly(benzyl methacrylate) in certain ionic liquids constitute unusual LCST systems, in that the second virial coefficient (A2) in dilute solutions has recently been shown to be positive, indicative of good solvent behavior, even above phase separation temperatures, where A2 < 0 is expected. In this work, we describe the LCST phase behavior of poly(benzyl methacrylate) in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide for three different molecular weights (32, 63, and 76 kg/mol) in concentrated solutions (5–40% by weight). Turbidimetry measurements reveal a strong concentration dependence to the phase boundaries, yet the molecular weight is shown to have no influence. The critical compositions of these systems are not accessed, and must therefore lie above 40 wt% polymer, far from the values (ca. 10%) anticipated by Flory-Huggins theory. The proximity of the experimental cloud point to the coexistence curve (binodal) and the thermo-reversibility of the phase transitions, are also confirmed at various heating and cooling rates.
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- Award ID(s):
- 1707578
- PAR ID:
- 10311034
- Date Published:
- Journal Name:
- Molecules
- Volume:
- 26
- Issue:
- 16
- ISSN:
- 1420-3049
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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