Synthesis and characterization of the conductivity and polarization processes in supported ionic liquid-like phases (SILLPs)

Different crosslinked polystyrene resins containing ionic liquid fragments covalently attached (supported ionic liquid-like phases: SILLPs) have been prepared and their conductivity has been studied by means of dielectric impedance spectroscopy. The main structural parameters considered in this study have been the presence of C2-H bonds in the imidazolium subunits and the nature (level of hydrophobicity) of the N-substituents (methyl vs. butyl). The results obtained show that the presence of C2-H fragments can have an influence on intrinsic conductivity. In the same way the role of the hydrophobicity of the N-substituents seems to play only a minor role. The main structural component associated with conductivity is the nature of the counteranion. The bulkiest, less coordinating anions, in particular the NTf2- anion, seem to be associated with the highest conductivities, with the values obtained being two orders of magnitude higher than those calculated for the same systems containing the Cl- anions for each of the temperatures under study. The results obtained rule out the participation of some given conduction mechanisms such as the involvement of carbene formation. Instead, the formation of ion-pairs of higher or lower association (strong/weak ion pairs) could be responsible for the observed behavior. (C) 2012 Elsevier B.V. All rights reserved.