Abstract
The study proposes using the distillable ionic liquid 5-methyl-1,5,7-triaza-bicyclo-[4.3.0]non-6-enium acetate, [mTBNH][OAc], for cellulose dissolution, making it an environmentally friendly alternative to conventional solvents in the transesterification of cellulose with vinyl esters. This ionic liquid (IL) has high dissolving power for cellulose and durability for recycling. However, its high viscosity limits cellulose concentration and its expensiveness hinders commercialization. The addition of naturally derived, low-cost, and low-viscous co-solvents can reduce overall cost and viscosity. In this study, various green co-solvents, including γ-valerolactone (GVL), dimethyl isosorbide (DMI), sulfolane (SLF), and N,N′-dimethylpropyleneurea (DMPU), were mixed with [mTBNH][OAc] to test their ability to enhance cellulose transesterification. Cellulose esters with a degree of substitution (DS) up to 1.6 have been synthesized. The chemical composition of the materials was confirmed by FTIR and NMR. Green co-solvents alter the solubility and flow activation energy of cellulose in binary solvents. The produced cellulose esters become more amorphous, and their viscosity and complex moduli decrease because of the DS changing in the following order: DMPU < SLF < DMI < GVL. The efficiency of internal plasticization of cellulose esters was studied through melt flow rheology, which indicated that it increases with increasing DS. All tested cellulose esters have almost identical degradation temperatures, as detected by TGA.
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NMR spectra were acquired on instrumentation of the Estonian Center of Analytical Chemistry (https://www.akki.ee, TT4).
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This research was funded by the Estonian Research Council, RESTA10.
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Conceptualization, E.T.; Validation, E.T.; Investigation, E.T., N.S., I.K., M.K., A.M., I.R., T.K., V.M., R.S.; Writing—original draft, E.T. and N.S.; Writing—review & editing, A.K.; Funding acquisition, A.K. The initial draft of the manuscript was written by E. Tarasova, and all authors reviewed and provided feedback on earlier versions. Finally, all authors read and approved the final manuscript.
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Tarasova, E., Savale, N., Trifonova, L. et al. Effect of green co-solvents on properties and synthesis of cellulose esters in superbase ionic liquid. Cellulose (2024). https://doi.org/10.1007/s10570-024-05920-x
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DOI: https://doi.org/10.1007/s10570-024-05920-x