DLP 3D Printing of Levoglucosenone‐Based Monomers: Exploiting Thiol‐ene Chemistry for Bio‐Based Polymeric Resins

Abstract

AbstractAdditive manufacturing (AM) is a well‐established technique that allows for the development of complex geometries and structures with multiple applications. While considered a more environmentally‐friendly method than traditional manufacturing, a significant challenge lies in the availability and ease of synthesis of bio‐based alternative resins. In our endeavor to valorize biomass, this work proposes the synthesis of new α,ω‐dienes derived from cellulose‐derived levoglucosenone (LGO). These dienes are not only straightforward to synthesize but also offer a tunable synthesis approach. Specifically, LGO is first converted into diol precursor, which is subsequently esterified using various carboxylic acids (in this case, 3‐butenoic, and 4‐pentenoic acids) through a straightforward chemical pathway. The resulting monomers were then employed in UV‐activated thiol‐ene chemistry for digital light process (DLP). A comprehensive study of the UV‐curing process was carried out by Design of Experiment (DoE) to evaluate the influence of light intensity and photoinitiator to find the optimal curing conditions. Subsequently, a thorough thermo‐mechanical characterization highlighted the influence of the chemical structure on material properties. 3D printing was performed, enabling the fabrication of complex and self‐stain structures with remarkable accuracy and precision. Lastly, a chemical degradation study revealed the potential for end‐of‐use recycling of the bio‐based thermosets.