Rheological and NMR Studies of Cellulose Dissolution in the Ionic Liquid BmimAc.
Katherine S LefroyBrent S MurrayMichael E RiesPublished in: The journal of physical chemistry. B (2021)
Solutions of two types of cellulose in the ionic liquid 1-butyl-3-methyl-imidazolium acetate (BmimAc) have been analyzed using rheology and fast-field cycling nuclear magnetic resonance (NMR) spectroscopy, in order to analyze the macroscopic (bulk) and microscopic environments, respectively. The degree of polymerization (DP) was observed to have a significant effect on both the overlap (c*) and entanglement (ce) concentrations and the intrinsic viscosity ([η]). For microcrystalline cellulose (MCC)/BmimAc solutions, [η] = 116 mL g-1, which is comparable to that of MCC/1-ethyl-3-methyl-imidazolium acetate (EmimAc) solutions, while [η] = 350 mL g-1 for the commercial cellulose (higher DP). Self-diffusion coefficients (D) obtained via the model-independent approach were found to decrease with cellulose concentration and increase with temperature, which can in part be explained by the changes in viscosity; however, ion interactions on a local level are also important. Both Stokes-Einstein and Stokes-Einstein-Debye analyses were carried out to directly compare rheological and relaxometry analyses. It was found that polymer entanglements affect the microscopic environment to a much lesser extent than for the macroscopic environment. Finally, the temperature dependencies of η, D, and relaxation time (T1) could be well described by Arrhenius relationships, and thus, activation energies (Ea) for flow, diffusion, and relaxation were determined. We demonstrate that temperature and cellulose concentration have different effects on short- and long-range interactions.