Interactions of two homologues of cationic surface active ionic liquids with sodium carboxymethylcellulose in aqueous solution

In the preceding paper of this series, we studied the interactions of copolymers with the ionic liquids, 1-alkyl-3-methylimidazolium bromide (C _n mimBr, n?=?8, 10, 12, 14, 16) and N-alkyl-N-methylpyrrolidinium bromide (C _n MPB, n?=?12, 14, 16). An obvious difference was detected between the interaction mechanism and the alkyl chain length of the surfactant. In the present study, we performed a systematic study on the interaction of sodium carboxymethylcellulose (NaCMC) with ionic liquids in aqueous solution by isothermal titration microcalorimetry (ITC), conductivity, turbidity, and dynamic light scattering (DLS) measurements. The existence of electrostatic attraction between NaCMC and ILs could increase the complexity of these systems. The results show that the monomers of C₈mimBr can bind to the NaCMC chains and form free surfactant micelles in the solution, while no micelle-like C₈mimBr/NaCMC cluster is detected. For other surfactants, the formation of surfactant/NaCMC clusters in the solution is driven by electrostatic and hydrophobic interactions, which could be divided into two types. One type is the polymer-induced surfactant/NaCMC complexes that form in the solution for the surfactant of C _n mimBr (n?=?10, 12, 14) or C _n MPB (n?=?12, 14). The other type is that the surfactant-induced surfactant/NaCMC complexes come into being for the surfactant of C₁₆mimBr or C₁₆MPB. Finally, the different modes of complex formation proposed have a good interpretation of the experiment results, unraveling the details of the effect of surfactant alkyl chain length and headgroup on the surfactant–NaCMC interactions.