Modes of Interaction in Binary Blends of HydrophobicPolyethers and Imidazolium Bis(trifluoromethylsulfonyl)imide IonicLiquids
2020
Lower critical solution
behavior in binary blends of hydrophobic
polyethers with 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
([hmim][Tf2N]) exhibited a difference in lower critical
solution temperature (LCST) greater than 80 °C between structurally
homologous poly(isopropyl glycidyl ether) (PiPGE) and poly(n-butyl glycidyl ether) (PnBGE). Replacement of the acidic
hydrogen on the imidazolium ring with a methyl group (i.e., 2,3-dimethyl-1-hexyl-imidazolium
bis(trifluoromethylsulfonyl)imide ([hmmim][Tf2N])) significantly
reduced the LCST of both the PnBGE/ionic liquid (IL) mixture and the
PiPGE/IL mixture. Differing degrees of hydrogen bonding between the
polymer and the cation cannot alone explain the observed behavior.
Similar hydrogen bonding between the [hmim]+ cation and
both polymers from molecular dynamics simulations was consistent with
this conclusion. However, stronger [hmim]+ cation tail/polymer
alkyl side-chain interactions for PnBGE, with consequently stronger
cation/anion interactions, point to solvophobic interactions as the
basis for the large LCST difference between the PnBGE/[hmim][Tf2N] and PiPGE/[hmim][Tf2N] blends.
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