Durable composites by vulcanization of oleyl-esterified lignin

Productive utilization of lignocellulosic biomass is critical to the continued advancement of human civilization. Whereas the cellulose component can be efficiently upconverted to automotive fuel-grade ethanol, the lack of upconversion methods for the lignin component constitutes one of the grand challenges facing science. Lignin is an attractive feedstock for structural applications, in which its highly-crosslinked architecture can endow composite structures with high strengths. Prior work suggests that high-strength composites can be prepared by the reaction of olefin-modified lignin with sulfur. Those studies were limited to <= 5 wt% lignin, due to phase-separation of hydrophilic lignin from hydrophobic sulfur matrices. Herein we report a protocol to increase lignin hydrophobicity and thus its incorporation into sulfur-rich materials. This improvement is affected by esterifying lignin with oleic acid prior to its reaction with sulfur. This approach allowed preparation of esterified lignin-sulfur (ELS) composites comprising up to 20 wt% lignin. Two reaction temperatures were employed such that the reaction of ELS with sulfur at 180 degrees C would only produce S-C bonds at olefinic sites, whereas the reaction at 230 degrees C would produce C-S bonds at both olefin and aryl sites. Mechanistic analyses and microstructural characterization elucidated two ELS composites having compressive strength values (>20 MPa), exceeding the values observed with ordinary Portland cements. Consequently, this new method represents a way to improve lignin utilization to produce durable composites that represent sustainable alternatives to Portland cements.

Automated summary

Productive utilization of lignocellulosic biomass is crucial, but the lack of upconversion methods for the lignin component is a major challenge. By esterifying lignin with oleic acid and reacting it with sulfur, a new protocol was developed to increase lignin hydrophobicity and incorporate it into sulfur-rich materials. The resulting esterified lignin-sulfur (ELS) composites exhibited high compressive strength values (>20 MPa) exceeding ordinary Portland cements, making them sustainable alternatives for durable composites.