Synthesis of a Liquid Lignin-Based Methacrylate Resin and Its Application in 3D Printing without Any Reactive Diluents.

3D printing of bio-based and renewable polymers such as lignin has gained research attention during the last few decades. We report on the synthesis and characterization of a liquid lignin-based photopolymer and its application in additive manufacturing (AM). Wheat straw soda lignin is liquified in an oxyalkylation reaction with propylene oxide under alkaline conditions and modified with methacryloyl chloride to obtain a lignin-based methacrylate resin. Ninety percent of the functional hydroxyl groups are grafted during the synthesis. The photopolymerization efficiency was evaluated by real-time-NIR-photorheology experiments with two different photoinitiators, leading to double bond conversions (DBC) of ≥80%. 3D-printing experiments of the methacrylated lignin were performed with the hot lithography technology. For the first time, a light-curable lignin derivative with a lignin content of over 30% was successfully 3D printed via vat photopolymerization without any reactive diluents, which is a significant improvement over current state-of-the-art solutions. This outstanding result is a motivating proof of concept and a promising starting point for the in-depth evaluation of bio-based precursors as an alternative to nonrenewable derivatives for 3D printing.

Visible Light Photoinitiator for 3D-Printing of Tough Methacrylate Resins.

Lithography-based additive manufacturing was introduced in the 1980s, and is still the method of choice for printing accurate plastic parts with high surface quality. Recent progress in this field has made tough photopolymer resins and cheap LED light engines available. This study presents the influence of photoinitiator selection and post-processing on the thermomechanical properties of various tough photopolymers. The influence of three photoinitiators (Ivocerin, BAPO, and TPO-L) on the double-bond conversion and mechanical properties was investigated by mid infrared spectroscopy, dynamic mechanical analysis and tensile tests. It was found that 1.18 wt % TPO-L would provide the best overall results in terms of double-bond conversion and mechanical properties. A correlation between double-bond conversion, yield strength, and glass transition temperature was found. Elongation at break remained high after post-curing at about 80-100%, and was not influenced by higher photoinitiator concentration. Finally, functional parts with 41 MPa tensile strength, 82% elongation at break, and 112 °C glass transition temperature were printed on a 405 nm DLP (digital light processing) printer.