Polymers (Basel). 2022 Oct 31;14(21):4637. doi: 10.3390/polym14214637.
Lignin-based chemicals and biomaterials will be feasible alternatives to their fossil-fuel-based counterparts once their breakdown into constituents is economically viable. The existing commercial market for lignin remains limited due to its complex heterogenous structure and lack of extraction/depolymerization techniques. Hence, in the present study, a novel low-cost ammonium-based protic ionic liquid (PIL), 2-hydroxyethyl ammonium lactate [N11H(2OH)][LAC], is used for the selective fractionation and improved extraction of lignin from Scots pine (Pinus sylvestris) softwood biomass (PWB). The optimization of three process parameters, viz., the incubation time, temperature, and biomass:PIL (BM:PIL) ratio, was performed to determine the best pretreatment conditions for lignin extraction. Under the optimal pretreatment conditions (180 °C, 3 h, and 1:3 BM:PIL ratio), [N11H(2OH)][LAC] yielded 61% delignification with a lignin recovery of 56%; the cellulose content of the recovered pulp was approximately 45%. Further, the biochemical composition of the recovered lignin and pulp was determined and the recovered lignin was characterized using 1H-13C heteronuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR) spectroscopy, quantitative 31P NMR, gel permeation chromatography (GPC), attenuated total reflectance (ATF)-Fourier transform infrared spectroscopy (ATR-FTIR), and thermal gravimetric analysis (TGA) analysis. Our results reveal that [N11H(2OH)][LAC] is significantly involved in the cleavage of predominant β-O-4′ linkages for the generation of aromatic monomers followed by the in situ depolymerization of PWB lignin. The simultaneous extraction and depolymerization of PWB lignin favors the utilization of recalcitrant pine biomass as feedstock for biorefinery schemes.