Effect of the Lignin Structure on the Physicochemical Properties of Lignin-Grafted-Poly(ϵ-caprolactone) and Its Application for Water/Oil Separation

Lignin-grafted poly(ϵ-caprolactone) copolymers (lignin-g-PCLs) have shown wide application potentials in coatings, biocomposites, and biomedical fields. However, the structural heterogeneity of lignin affecting the structures and properties of lignin-g-PCL has been scarcely investigated. Herein, kraft lignin is fractionated into four precursors, namely, F_ins, F1, F2, and F3, with declining molecular weights and increased hydroxyl contents. Lignin-g-PCLs are synthesized via ring-opening polymerization of ϵ-caprolactone with lignin and characterized by GPC, FTIR, ¹H and ³¹P NMR, DSC, TGA, and iGC. The mechanical properties, UV barrier, and enzymatic biodegradability of the lignin-g-PCLs are evaluated. Results show that lignin with a higher molecular weight and aliphatic OH favors the copolymerization, leading to lignin-g-PCLs with longer PCL arms. Moreover, lignin incorporation improves the thermal stability, hydrophobicity, and UV-blocking ability but reduces the lipase hydrolyzability of the copolymers. We also demonstrated that the lignin-g-PCL-coated filter paper could successfully separate chloroform-, petroleum ether-, and hexane-water mixtures with an efficiency up to 99.2%. The separation efficiency remains above 90% even after 15 cycles. The structural differences of copolymers derived from the fractionation showed minimal influence on the separation efficiency. This work provides new insights into lignin-based copolymerization and the versatility of lignin valorization. copy; 2022 American Chemical Society.