Polymerization of Monomeric Ionic Liquid Confined within Uniaxial Alumina Pores as a New Way of Obtaining Materials with Enhanced Conductivity

Broadband dielectric spectroscopy (BDS) and differential scanning calorimetry (DSC) have been employed to probe dynamics and charge transport of 1-butyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide ([bvim][NTf₂]) confined in native uniaxial AAO pores as well as to study kinetics of radical polymerization of the examined compound as a function of the degree of confinement. Subsequently, the electronic conductivity of the produced polymers was investigated. As observed, polymerization carried out at T = 363 K proceeds faster under confinement with some saturation effect observed for the sample in pores of smaller diameter. Obtained results were discussed in the context of the very recent reports showing that the free volume of the confined material is higher with respect to the bulk one. It was also noted that conductivity of poly[bvim][NTf₂] is significantly higher with respect to the macromolecules obtained upon bulk polymerization. Moreover, charge transport of the confined macromolecules is even higher when compared to the bulk monomeric ionic liquid at some thermodynamic conditions. Additionally, the molecular weight, M_w, of the confined-synthesized polymers is significantly higher with respect to the bulk-synthesized material. Interestingly, both parameters, (i) the enhancement of σ_dc and (ii) the increase in M_w, can be tuned and controlled by the application of the appropriate confinement. Consequently, those results are quite promising in the context of development of the fabrication of polymerized ionic liquids (PILs) nanomaterials with unique properties and morphologies, which can be further easily applied in the field of nanotechnology.