Lignin‐Based Materials Through Thiol–Maleimide “Click” Polymerization

Abstract In the present report an environmentally friendly approach to transforming renewable feedstocks into value‐added materials is proposed. This transformation pathway was conducted under green conditions, without the use of solvents or catalyst. First, controlled modification of lignin, a major biopolymer present in wood and plants, was achieved by esterification with 11‐maleimidoundecylenic acid (11‐MUA), a derivative from castor oil that contains maleimide groups, following its transformation into 11‐maleimidoundecanoyl chloride (11‐MUC). Different degrees of substitution were achieved by using various amounts of the 11‐MUC, leading to an efficient conversion of lignin hydroxy groups, as demonstrated by 1 H and 31 P NMR analyses. These fully biobased maleimide‐lignin derivatives were subjected to an extremely fast (ca. 1 min) thiol–ene “click” polymerization with thiol‐containing linkers. Aliphatic and aromatic thiol linkers bearing two to four thiol groups were used to tune the reactivity and crosslink density. The properties of the resulting materials were evaluated by swelling tests and thermal and mechanical analyses, which showed that varying the degree of functionality of the linker and the linker structure allowed accurate tailoring of the thermal and mechanical properties of the final materials, thus providing interesting perspectives for lignin in functional aromatic polymers.