Sustainable polymers from lignocellulosic biomass have the potential to reduce the environmental impact of commercial plastics while also offering significant performance and cost benefits relative to petrochemical-derived macromolecules. However, most currently available biobased polymers are hampered by insufficient thermomechanical properties, low economic feasibility (e.g., high relative cost), and reduced scalability in comparison to petroleum-based incumbents. Future biobased materials must overcome these limitations to be competitive in the marketplace. Additionally, sustainability challenges at the beginning and end of the polymer lifecycle need to be addressed using green chemistry practices and improved end-of-life waste management strategies. This viewpoint provides an overview of recent developments that can mitigate many concerns with present materials and discusses key aspects of next-generation, biobased polymers derived from lignocellulosic biomass.

Renewable and sustainable thermosets with thermomechanical properties that are equivalent to, or better than, those of petroleum-derived commercial incumbents are desirable to mitigate environmental and human health impacts. Current bioderivable or biobased thermosets typically are aliphatic/cycloaliphatic and lack the robust structural features necessary to generate materials competitive with those made from conventional aromatics such as bisphenol A. Lignocellulosic biomass (LCB) is the most abundant, renewable feedstock for the production of platform aromatic chemicals (e.g., phenolics from lignin, furanics from cellulosics) which are ideal as sustainable, biobased alternatives to petroleum-derived constituents for high-performance applications. This Perspective provides an overview of LCB-derivable aromatic monomers, including epoxies, cyanate esters, vinyl esters, benzoxazines, and cyclic carbonates, and it benchmarks the corresponding materials against commercially available thermosets. Furthermore, green synthesis approaches to minimize environmental impacts, robust processing methods to increase versatility, structure−property relationships to guide materials design, and life-cycle management strategies to improve the recyclability of thermosets are discussed, along with additional avenues to advance the commercial relevance of biobased thermosets. For instance, the positive impacts of the inherent functionality in biobased monomers on toxicity and environmental considerations, as well as opportunities to leverage the synergies between experimental and computational activities, are highlighted.

Chemocatalytic lignin valorization strategies are critical for a sustainable bioeconomy, as lignin, especially technical lignin, is one of the most available and underutilized aromatic feedstocks. Here, we provide the first report of an intensified reactive distillation–reductive catalytic deconstruction (RD-RCD) process to concurrently deconstruct technical lignins from diverse sources and purify the aromatic products at ambient pressure. We demonstrate the utility of RD-RCD bio-oils in high-performance additive manufacturing via stereolithography 3D printing and highlight its economic advantages over a conventional reductive catalytic fractionation/RCD process. As an example, our RD-RCD reduces the cost of producing a biobased pressure-sensitive adhesive from softwood Kraft lignin by up to 60% in comparison to the high-pressure RCD approach. Last, a facile screening method was developed to predict deconstruction yields using easy-to-obtain thermal decomposition data. This work presents an integrated lignin valorization approach for upgrading existing lignin streams toward the realization of economically viable biorefineries.

We introduce the oxidation of long aliphatic alkanes using non-thermal, atmospheric plasma processing as an eco-friendly route for organic synthesis. A pulsed dielectric barrier discharge in He/O2 gas mixtures was employed to functionalize n-octadecane. C18 secondary alcohols and ketones were the main products, with an optimal molar yield of ∼29.2%. Prolonged treatment resulted in the formation of dialcohols, diketones, and higher molecular weight oxygenates. Lighter hydrocarbon products and decarboxylation to CO2 were also observed at longer treatment times and higher power inputs. A maximum energy yield of 5.48 × 10–8 mol/J was achieved at short treatment times and high powers, associated with higher selectivity to primary oxygenates. Direct hydroxylation of alkyl radicals, as well as disproportionation reactions, are proposed as the main pathways to alcohols and ketones. The results hold promise for functionalizing long hydrocarbon molecules at ambient conditions using catalyst-free plasma discharges.

Alternative polymer feedstocks are highly desirable to address environmental, social, and security concerns associated with petrochemical-based materials. Lignocellulosic biomass (LCB) has emerged as one critical feedstock in this regard because it is an abundant and ubiquitous renewable resource, which can be deconstructed to generate valuable fuels, chemicals, and small molecules/oligomers that are amenable to modification and polymerization. However, the diversity of LCB complicates the evaluation of biorefinery concepts in areas including process scale-up, production outputs, plant economics, and life-cycle management. We discuss aspects of current LCB biorefinery research with a focus on the major process stages, including feedstock selection, fractionation/deconstruction, and characterization, along with product purification, functionalization, and polymerization to manufacture valuable macromolecular materials. We highlight opportunities to valorize underutilized and complex feedstocks, leverage advanced characterization techniques to predict and manage biorefinery outputs, and increase the fraction of biomass converted into valuable products. Expected final online publication date for the Annual Review of Chemical and Biomolecular Engineering, Volume 14 is June 2023. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.