Chemical modification of lignins: Towards biobased polymers

Lignins are now considered as the main aromatic renewable resource. They represent an excellent alternative feedstock for the elaboration of chemicals and polymers. Lignin is a highly abundant biopolymeric material that constitutes with cellulose one of the major components in structural cell walls of higher vascular plants. Large quantities of lignin are yearly available from numerous pulping processes such as paper and biorefinery industries. Lignin extraction from lignocellulosic biomass (wood, annual plant) represents the key point to its large use for industrial applications. One of the major problems still remains is its unclearly defined structure and its versatility according to the origin, separation and fragmentation processes, which mainly limits its utilization. While currently often used as a filler or additive, lignin is rarely exploited as a raw material for chemical production. However, it may be an excellent candidate for chemical modifications and reactions due to its highly functional character (i.e., rich in phenolic and aliphatic hydroxyl groups) for the development of new biobased materials. Chemical modification of lignin has driven numerous efforts and researches with significant studies during the last decades. After an overview with some generalities concerning the main extraction techniques along with the structure and the properties of lignins, this review describes in details the different chemical modifications of lignins. They are classified into three groups: (1) lignin fragmentation into phenolic or other aromatic compounds for fine chemistry, (2) synthesis of new chemical active sites to impart new reactivity to lignin, and (3) functionalization of hydroxyl groups to enhance their reactivity. In that frame, the potential applications of lignin as precursor for the elaboration of original macromolecular architecture and the development of new building blocks are discussed. Finally, the major achievements and remaining challenges for lignin modifications and its uses as a macromer for polymer synthesis are also mentioned with emphasis on the most promising and relevant applications.