Allylation and Thermosetting of Acetosolv Wheat Straw Lignin

The acetosolv extraction, allylation and subsequent cross-linking of wheat straw lignin to thermoset biomaterials is herein described. The extraction temperature proved to be of great importance for the quality of the resulting lignin, with moderate temperature being key for preservation of β-O-4' linkages. The allylation of the acetosolv lignin was carried out using three different synthetic strategies, resulting in selective installation of either benzylic or phenolic allyl ethers, or unselective allylation of various hydroxyl groups via etherification and carboxyallylation. The different allylation protocols employed either allyl alcohol, allyl chloride, or diallylcarbonate as allyl precursors where the latter gave the highest degree of functionality. The results also show that it is crucial to choose a functionalization protocol that is adapted to the functional groups present in the specific lignin used. Selected allylated acetosolv lignins were cross-linked using a thiol-ene approach and the lignin with the highest density of allyl groups was found to form a cross-linked thermoset material with properties comparable to kraft lignin-based analogues.