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.

Vinyl Sulfonate Esters: Efficient Chain Transfer Agents for the 3D Printing of Tough Photopolymers without Retardation.

The formation of networks through light-initiated radical polymerization allows little freedom for tailored network design. The resulting inhomogeneous network architectures and brittle material behavior of such glassy-type networks limit the commercial application of photopolymers in 3D printing, biomedicine, and microelectronics. An ester-activated vinyl sulfonate ester (EVS) is presented for the rapid formation of tailored methacrylate-based networks. The chain transfer step induced by EVS reduces the kinetic chain length of the photopolymer, thus shifting the gel point to higher conversion, which results in reduced shrinkage stress and higher overall conversion. The resulting, more homogeneous network is responsible for the high toughness of the material. The unique property of EVS to promote nearly retardation-free polymerization can be attributed to the fact that after the transfer step no polymerizable double bond is formed, as is usually seen in classical chain transfer agents. Laser flash photolysis, theoretical calculations, and photoreactor studies were used to elucidate the fast chain transfer reaction and exceptional regulating ability of EVS. Final photopolymer networks exhibit improved mechanical performance making EVS an outstanding candidate for the 3D printing of tough photopolymers.