Lignin polymerization: towards high-performance materials

Lignocellulosic biomass is the only sufficiently available resource for the sustainable development of the bioeconomy. Among the main components of lignocellulose, lignin has a tremendous potential to serve as a natural aromatic polymer resource due to the vast amounts of lignin available from industrial processes. However, commercial application of lignin is still limited and represents only a minor fraction of the potential utilization of approximately 20 million tons that can readily be isolated from spent pulping liquors and obtained as a residue from lignocellulosic biorefineries. Industrial processes generally depolymerize lignin into heterogeneous mixtures of low molecular weight macromolecules with a high degree of condensation, which collectively makes it challenging to develop them into high-performance materials. Although often neglected, some of the major limitations of these so-called technical lignins are their low molar mass and high dispersity, which make these lignins have poor mechanical properties. The polymerization of small lignin fragments not only contributes to the development of high-performance and multifunctional advanced materials, but also helps to improve the fundamental theory of lignin polymer chemistry. In this review, the polymerization of lignin via physical (aggregation), chemical (chain extension, cross-linking, and grafting), and biological (enzymatic polymerization) routes is described, its applications are assessed, and prospects for the development of high-performance lignin polymer materials are discussed.