One-pot synthesis of thermally reversible materials using maleimide-polysaccharide and furan-lignin derivatives

Abstract

The bio-based materials potato starch (St) and Kraft lignin (KL) were chemically modified to create a thermally responsive network through a reversible Diels–Alder (DA) reaction between maleimide and furan groups present in St and KL, respectively. To achieve this, St was esterified in a one-pot synthesis at room temperature with 6-maleimidohexanoic acid (6-MHA) to produce St 6MHA aligning with the 12 principles of green chemistry, which was confirmed by FTIR, ¹H, ¹³C, and 2D NMR spectroscopy. Furan (Fu) groups were introduced to KL by reacting furfuryl glycidyl ether with the phenol entities of KL, forming KL-Fu. The structures of the KL-Fu derivatives were characterized using FTIR, ¹H, ¹³C, and ³¹P spectroscopy, as well as TGA. St 6-MHA and KL-Fu were then subjected to thermal cycloaddition through the DA reaction. Furthermore, controlled retro-DA reactions were induced thermally and confirmed by FTIR and ¹H NMR spectroscopy. DSC analysis of the final products revealed the thermally responsive nature of the system. This study highlights the significant potential of such a thermally responsive system, demonstrating that effective chemical modification of abundant renewable feedstock can enable the development of high-value materials thereof.