Search Results (4)

The transesterification of cellulose with vinyl esters in ionic liquid media is suggested as a prospective environmentally friendly alternative to conventional esterification. In this study, various long-chain cellulose esters (laurate, myristate, palmitate, and stearate) with a degree of substitution (DS) up to 1.8 have been synthesized in novel distillable ionic liquid, [mTBNH][OAC]. This IL has high dissolving power towards cellulose, which can improve homogeneous transesterification. Additionally, [mTBNH][OAC] has durability towards recycling and can be regenerated and re-used again for the next cycles of esterification. DMSO is used as a co-solvent because of its ability to speed up mass transport due to lower solvent viscosity. The optimization of the reaction parameters, such as co-solvent content, temperature (20–80 °C), reaction time (1–5 h), and a molar ratio of reactants (1–5 eq. AGU) is reported. It was found that within studied reaction conditions, DS increases with increasing reaction time, temperature, and added vinyl esters. Structure analysis using FTIR, ¹H, and ¹³C NMR after acylation revealed the introduction of the alkyl chains into cellulose for all studied samples. The results also suggested that the substitution order of the OH group is C7-O6 > C7-O2 > C7-O3. Unique, complex thermal and rheological investigation of the cellulose esters shows the growth of an amorphous phase upon the degree of substitution. At the same time, the homogeneous substitution of cellulose with acyl chains increases the melt viscosity of a material. Internal plasticization in cellulose esters was found to be the mechanism for the melt processing of the material. Long-chain cellulose esters show the potential to replace commonly used externally plasticized cellulose derivatives. Full article

Due to environmental concerns, more attention has been given to the development of bio-based materials for substitution of fossil-based ones. Moreover, paper use is essential in daily routine and several applications of industrial pulp can be developed. In this study, transparent films were produced by industrial cellulose pulp solubilization in tetramethylguanidine based ionic liquids followed by its regeneration. Films were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), UV/Vis spectroscopy, proton nuclear magnetic resonance (¹H-NMR), dynamic scanning calorimetry (DSC), thermal analysis (TG), and X-ray diffraction (XRD). Mechanical tests showed that films have a good elongation property, up to 50%, depending on ionic liquid incorporation. The influence of the conjugated acid and dissolution temperature on mechanical properties were evaluated. These results revealed the potential of this methodology for the preparation of new biobased films. Full article

Herein, we report on the metal-free, one-pot synthesis of industrially important dimethyl carbonate (DMC) from molecular CO₂ under ambient conditions. In this process, initially the CO₂ was chemisorbed through the formation of a switchable ionic liquid (SIL), [DBUH] [CH₃CO₃], by the interaction of CO₂ with an equivalent mixture of organic superbase 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and methanol. The obtained SIL further reacted with methyl iodide (CH₃I) to form DMC. The synthesis was carried out in both dimethyl sulfoxide (DMSO) and methanol. Methanol is preferred, as it not only served as a reagent and solvent in CO₂ capture and DMC synthesis, but it also assisted in controlling the side reactions between chemical species such as CH₃I and [DBUH]⁺ cation and increased the yield of DMC. Hence, the use of methanol avoided the loss of captured CO₂ and favored the formation of DMC with high selectivity. Under the applied reaction conditions, 89% of the captured CO₂ was converted to DMC. DBU was obtained, achieving 86% recovery of its salts formed during the synthesis. Most importantly, in this report we describe a simple and renewable solvent-based process for a metal-free approach to DMC synthesis under industrially feasible reaction conditions. Full article

This review is focused on assessment of solvents for cellulose dissolution and the mechanism of regeneration of the dissolved biopolymer. The solvents of interest are imidazole-based ionic liquids, quaternary ammonium electrolytes, salts of super-bases, and their binary mixtures with molecular solvents. We briefly discuss the mechanism of cellulose dissolution and address the strategies for assessing solvent efficiency, as inferred from its physico-chemical properties. In addition to the favorable effect of lower cellulose solution rheology, microscopic solvent/solution properties, including empirical polarity, Lewis acidity, Lewis basicity, and dipolarity/polarizability are determinants of cellulose dissolution. We discuss how these microscopic properties are calculated from the UV-Vis spectra of solvatochromic probes, and their use to explain the observed solvent efficiency order. We dwell briefly on use of other techniques, in particular NMR and theoretical calculations for the same purpose. Once dissolved, cellulose is either regenerated in different physical shapes, or derivatized under homogeneous conditions. We discuss the mechanism of, and the steps involved in cellulose regeneration, via formation of mini-sheets, association into “mini-crystals”, and convergence into larger crystalline and amorphous regions. We discuss the use of different techniques, including FTIR, X-ray diffraction, and theoretical calculations to probe the forces involved in cellulose regeneration. Full article