Lignin-based smart materials are emerging into advanced material applications as stimuli-responsive actuators, sensors, controlled release systems, and more.

Biobased circular materials are alternatives to fossil-based engineering plastics, but simple and material-efficient synthetic routes are needed for industrial scalability. Here, a series of lignin-based vitrimers built on dynamic acetal covalent networks with a gel content exceeding 95% were successfully prepared in a one-pot, thermally activated, and catalyst-free “click” addition of softwood kraft lignin (SKL) to poly(ethylene glycol) divinyl ether (PDV). The variation of the content of lignin from 28 to 50 wt % was used to demonstrate that the mechanical properties of the vitrimers can be widely tuned in a facile way. The lowest lignin content (28 wt %) showed a tensile strength of 3.3 MPa with 35% elongation at break, while the corresponding values were 50.9 MPa and 1.0% for the vitrimer containing 50 wt % of lignin. These lignin-based vitrimers also exhibited excellent performance as recoverable adhesives for different substrates such as aluminum and wood, with a lap shear test strength of 6.0 and 2.6 MPa, respectively. In addition, recyclability of the vitrimer adhesives showed preservation of the adhesion performance exceeding 90%, indicating a promising potential for their use in sustainable circular materials.

ConspectusThe increasing demand for polymeric materials derived from petroleum resources, along with rising concerns about climate change and global plastic pollution, has driven the development of biobased polymeric materials. Lignin, which is the second most abundant biomacromolecule after cellulose, represents a promising renewable raw material source for the preparation of advanced materials. The lucrative properties of lignin include its high carbon content (>60 atom %), high thermal stability, biodegradability, antioxidant activity, absorbance of ultraviolet radiation, and slower biodegradability compared to other wood components. Moreover, the advent of lignin nanoparticles (LNPs) over the last ten years has circumvented many well-known shortcomings of technical lignins, such as heterogeneity and poor compatibility with polymers, thereby unlocking the great potential of lignin for the development of advanced functional materials.LNPs stand out owing to their well-defined spherical shape and excellent colloidal stability, which is due to the electrostatic repulsion forces of carboxylic acid and phenolic hydroxyl groups enriched on their surface. These forces prevent their aggregation in aqueous dispersions (pH 3-9) and provide a high surface area to mass ratio that has been exploited to adsorb positively charged compounds such as enzymes or polymers. Consequently, it is not surprising that LNPs have become a prominent player in applied research in areas such as biocatalysis and polymeric composites, among others. However, like all ventures of life, LNPs also face certain challenges that limit their potential end-uses. Solvent instability remains the most challenging aspect due to the tendency of these particles to dissolve or aggregate in organic solvents and basic or acidic pH, thus limiting the window for their chemical functionalization and applications. In addition, the need for organic solvent during their preparation, the poor miscibility with hydrophobic polymeric matrices, and the nascent phase regarding their use in smart materials have been identified as important challenges that need to be addressed.In this Account, we recapitulate our efforts over the past years to overcome the main limitations mentioned above. We begin with a brief introduction to the fundamentals of LNPs and a detailed discussion of their associated challenges. We then highlight our work on: (i) Preparation of lignin-based nanocomposites with improved properties through a controlled dispersion of LNPs within a hydrophobic polymeric matrix, (ii) Stabilization of LNPs via covalent (intraparticle cross-linking) and noncovalent (hydration barrier) approaches, (iii) The development of an organic-solvent-free method for the production of LNPs, and (iv) The development of LNPs toward smart materials with high lignin content. Finally, we also offer our perspectives on this rapidly growing field.

Synthetic polymers are indispensable in many different applications, but there is a growing need for green processes and natural surfactants for emulsion polymerization. The use of solid particles to stabilize Pickering emulsions is a particularly attractive avenue, but oxygen sensitivity has remained a formidable challenge in controlled polymerization reactions. Here we show that lignin nanoparticles (LNPs) coated with chitosan and glucose oxidase (GOx) enable efficient stabilization of Pickering emulsion and in situ enzymatic degassing of single electron transfer-living radical polymerization (SET-LRP) without extraneous hydrogen peroxide scavengers. The resulting latex dispersions can be purified by aqueous extraction or used to obtain polymer nanocomposites containing uniformly dispersed LNPs. The polymers exhibit high chain-end fidelity that allows for production of a series of well-defined block copolymers as a viable route to more complex architectures.

Coating of lignin nanoparticles with chitosan and glucose oxidase allows for the green synthesis of acrylic and vinyl polymers in Pickering emulsions. The resulting dispersions offer a green route to tough composites equipped with antioxidant activity.

Lignin nanoparticles (LNPs) are promising renewable nanomaterials with applications ranging from biomedicine to water purification. However, the instability of LNPs under acidic and basic conditions severely limits their functionalization for improved performance. Here, we show that controlling the degree of esterification can significantly improve the stability of lignin oleate nanoparticles (OLNPs) in acidic and basic aqueous dispersions. The high stability of OLNPs is attributed to the alkyl chains accumulated in the shell of the particle, which delays protonation/deprotonation of carboxylic acid and phenolic hydroxyl groups. Owing to the enhanced stability, acid‐ and base‐catalyzed functionalization of OLNPs at pH 2.0 and pH 12.0 via oxirane ring‐opening reactions were successfully performed. We also demonstrated these new functionalized particles as efficient pH‐switchable dye adsorbents and anticorrosive particulate coatings.