Multiple Relaxations and Entanglement Behaviors of Polymerized Ionic Liquids with Various Anions/Cations

Polymerized ionic liquids (PILs) with anions of bis(trifluoromethylsulfonyl)imide (TFSI-), hexafluorophosphate (PF6-), and tetrafluoroborate (BF4-) and cations of poly[1-(4-vinylbenzyl)-3-alkyl-imidazolium] P[VBCnIM](+) with alkyl lengths C-1, C-2, and C-4 were successfully synthesized and characterized. X-ray scattering showed an increase in backbone-to-backbone spacing (d(b)) by 0.8 & Aring; per CH2 added to the alkyl side chain. Rheological and dielectric measurements were used to measure rates of chain relaxation and ion dissociation/association. The glass transition temperatures T-g follow the trend: PC4-TFSI < PC2-TFSI < PC1-TFSI < PC1-BF4 < PC1-PF6, which correlates well with their dielectric behaviors. However, the fragility m(DR) from dielectric relaxation increases with decreasing T-g, which is the opposite of the dependence of fragility m(Rheo) from rheology for both our PILs and neutral polymers. The dielectric and rheological relaxations of our PILs are expected to be influenced by both their anion-cation binding energies and their relative free volumes, while for neutral polymers, relaxations are primarily governed by free volume. The increase of fragility of m(DR) with decreasing T-g, therefore, suggests that dielectric relaxation is influenced more by anion-cation binding energy than by free volume, while the reverse is true for m(Rheo). The plateau modulus G(N) and entanglement molecular weight M-e estimated from rheological measurements agree with predictions of the packing model, using only a small modification of the Flory characteristic ratio C-infinity from that of a neutral polymer. Packing lengths of p = 6.0 similar to 9.3 & Aring; and tube diameters d(t) = 11 similar to 17 nm are found, depending on specific cation and anion structures.