Synthesis and Characterization of Caprolactam- based Ionic Liquids as Green Solvents

Abstract

Aims: To synthesize and characterize six caprolactam-based ionic liquids (CPILs) by combination of caprolactam with different organic and inorganic Brønsted acids that can be utilized for lipid extraction from microalgae.
 Study design: Experimental design include quantitative and qualitative.
 Place and duration of study: The study was done at Department of Chemistry & Biochemistry, School of Sciences and Aerospace Studies, Moi University (Kenya) between November 2020 and May 2021.
 Methodology: Six CPILs were prepared through a simple neutralization reaction between Caprolactam and Brønsted acids such as Hydrochloric acid (HCl), Methane sulphonic acid (CH3SO3H), Trifluoromethanesulphonic acid (CF3SO3H), Acetic acid (CH3CO2H), Trifluoroacetic acid (CF3CO2H), and Sulfuric acid (H2SO4). The first three acids were used in the synthesis of CPILs for the first time. The chemical structures of the synthesized CPILs were characterized by Fourier transform infrared and Raman spectroscopy. The densities and viscosities were measured at 20 oC using the weight (pycnometer) and capillary viscometer (Oswald) methods, respectively.
 Results: All the CPILs were insoluble in hexane and had high miscibility with water and methanol. Fourier transform infrared and Raman spectra of the CPILs were compared with that of free Caprolactam. The characteristic absorption bands of the synthesized compounds showed a big shift in position and/or intensity (compared to caprolactam), indicating the formation of the CPILs. The results showed that both the density and viscosity increased with the molecular weight of the anion - except in Caprolactamium hydrogen sulphate (CPSA)- which could be due to the strong interactions between the cation and anion resulting from the dimerization between hydrogen sulphate anions. 
 Conclusion: The hydrophilic nature of the CPILs indicated by high miscibility with polar solvents (water and methanol) indicates that they are suitable for the dissolution of cellulose of microalgae cell wall and thus could result in high lipid extraction efficiency. Further studies should therefore utilize the synthesized CPILs in lipid extraction from microalgae.

Lipid extraction from microalgae using pure caprolactam-based ionic liquids and with organic co-solvent

“…The CPILs used for lipid extraction experiments are listed in (Table 1), and were synthesized by adding equimolar quantities of caprolactam and an acid (hydrochloric, methane sulphonic, trifluoromethanesulphonic, acetic, Trifluoroacetic, and sulfuric), followed by stirring at room temperature for 24 h. Four of these ILs are liquids at room temperature, namely CPAA, CPSA, CPTFA and CPTFS. The methodologies for synthesis and characterization are explained in detail elsewhere in the literature (Naiyl et al, 2021).…”

“…To establish whether it is possible to improve the long-term viability and sustainability of the extraction procedure for lipids, we have investigated the effectiveness and efficiency of six CPILs-Caprolactamium chloride (CPHA), Caprolactamium methyl sulphonate (CPMS), Caprolactamium trifluoromethane sulfonate (CPTFS), Caprolactamium acetate (CPAA), Caprolactamium hydrogen sulphate (CPSA) and Caprolactamium trifluoromethane-acetate (CPTFA)-for extraction of lipids from wet and dry S. platensis microalgae biomass. Of these, the first three are novel ILs (Naiyl et al, 2021), whereas the others-except for Caprolactam acetate-were used for the first time in lipids' extraction. Extractions with both pure ionic liquids and ionic liquids/methanol mixtures were done to establish whether organic co-solvents could improve lipid extraction yields.…”