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Lignins are the most important aromatic renewable natural resource today, serving as a sustainable, environmentally acceptable alternative feedstock to fossil-derived chemicals and polymers in a vast scope of value-added applications. Lignin is a biopolymeric molecule that, together with cellulose, is a fundamental component of higher vascular plants structural cell walls. It can be extracted from by-products of the pulp and paper industries, agricultural waste and residues, and biorefinery products. Lignin properties may vary depending on source and extraction method with carbon and aromatic as the main compositions in lignin structure. These rich compositions make lignin more valuable, allowing for the creation of high-value-added green composites. However, the complex structure of lignin creates low reactivity to interact with crosslinker, and hence chemical modification is substantial to overcome this problem. This review aimed to present and discuss lignin structure, variation of lignin chemical properties regarding its source and extraction process, recent advances in chemical modification of lignin to enhance its reactivity, and potential applications of modified lignin for manufacturing value-added biocomposites with enhanced properties and lower environmental impact, such as food handling/packaging, seed coating, automotive devices, 3D printing, rubber industry, and wood adhesives.

For the transition towards greener biorefineries with reduced waste, valorization of lignin to drop‐in chemicals instead of their combustion for energy purposes is a key issue for future processes. In this context, lignin should be extracted from lignocellulosic biomass (LCB) and fragmented into smaller units, followed by catalytic funneling to fine chemicals. In this review, we report on the classical approaches for lignin valorization from LCB: thermal treatments, solvolytic valorization, acid‐catalyzed process, and base‐catalyzed process. We also provide the reader with the modern approach of lignin valorization that led to an integrated LCB biorefinery. The performance of different solid catalysts in lignin‐first approach via reductive or oxidative catalytic fractionation at different conditions is discussed in detail.

Lignin is the by-product of pulp and paper industries and bio-refining operations. It is available as the leading natural phenolic biopolymer in the market. It has chromophore functional groups and can absorb a broad spectrum of UV light in range of 250–400 nm. Using lignin as a natural ingredient in sunscreen cream, transparent film, paints, varnishes and microorganism protection has been actively investigated. Both in non-modified and modified forms, lignin provides enhancing UV protection of commercial products with less than a 10% blend with other material. In mixtures with other synthetic UV blockers, lignin indicated synergic effects and increased final UV blocking potential in compare with using only synthetic UV blocker or lignin. However, using lignin as a UV blocker is also challenging due to its complex structure, polydispersity in molecular weight, brownish color and some impurities that require more research in order to make it an ideal bio-based UV blocker.

Switchgrass was pretreated with sodium hydroxide (NaOH) at various concentrations and pretreatment times to investigate how delignification caused by NaOH affects its lignin chemistry. NaOH resulted in significant delignification ranging from 44.0 to 84.6% depending on pretreatment intensity. While there was no significant glucan loss due to NaOH pretreatment, higher NaOH concentrations removed xylan by up to 28.3%. Nitrobenzene oxidation (NBO) was used to study changes in lignin chemistry, and indicated that at higher NaOH concentrations, the amount of 4-hydroxygenzaldehyde (Hy) degraded from p-hydroxyphenyl propanol (H) lignin units was significantly reduced (p < 0.05). However, amounts of syringic (SA) and vanillic (VA) acids generated from syringyl (S) and guaiacyl (G) degradation were greater at higher NaOH concentration. S/G ratio (=0.62 raw switchgrass) did not significantly (p > 0.05) change with 15 min pretreatment, but it increased to 0.75 and 0.72, respectively, with 30 and 60 min pretreatments (p < 0.05). Increase in NaOH concentration did not significantly (p > 0.05) change S/G ratio, but H/G ratio (=0.48 raw switchgrass) decreased significantly to 0.14 regardless of pretreatment times. Overall, the H unit was found to be more susceptible to NaOH than S and G unit monolignols. Though changes in lignin chemistry due to NaOH concentration were observed, their impact on cellulolytic enzyme action during hydrolysis could not be fully understood. Further studies on lignin isolation may help to determine how these changes in lignin chemistry by NaOH impact cellulolytic enzymes.