Toward Circular Recycling of Polyurethanes: Depolymerization and Recovery of Isocyanates.

We report a depolymerization strategy to nearly quantitatively regenerate isocyanates from thermoplastic and thermoset polyurethanes (PUs) and then resynthesize PUs using the recovered isocyanates. To date, chemical/advanced recycling of PUs has focused primarily on the recovery of polyols and diamines under comparatively harsh conditions (e.g., high pressure and temperature), and the recovery of isocyanates has been difficult. Our approach leverages an organoboron Lewis acid to depolymerize PUs directly to isocyanates under mild conditions (e.g., ∼80 °C in toluene) without the need for phosgene or other harsh reagents, and we show that both laboratory-synthesized and commercially sourced PUs can be depolymerized. Furthermore, we demonstrate the utility of the recovered isocyanate in the production of second-generation PUs with thermal properties and molecular weights similar to those of the virgin PUs. Overall, this route uniquely provides an opportunity for circularity in PU materials and can add significant value to end-of-life PU products.

Engineering Innovations, Challenges, and Opportunities for Lignocellulosic Biorefineries: Leveraging Biobased Polymer Production.

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. LCB 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.

Ambient-pressure lignin valorization to high-performance polymers by intensified reductive catalytic deconstruction.

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 distillation­reductive 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.

100th Anniversary of Macromolecular Science Viewpoint: Polymers from Lignocellulosic Biomass. Current Challenges and Future Opportunities.

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.