Green chemistry and green engineering concepts have been combined to develop novel sustainable polymeric materials. Solvent free photocurable acrylate resins with biorenewable carbon content of 75%–82% suitable for application in DLP 3D printing technology were composed by commercially available bio‐based materials, acrylated epoxidized soybean oil (AESO), isobornyl methacrylate (IBOMA), methacrylic ester (ME), tetrahydrofurfuryl acrylate (THFA), and tetrahydrofurfuryl methacrylate (THFMA). They demonstrated high printing accuracy and good adhesion between layers. The monitoring of photocross‐linking kinetics of high biorenewable content acrylate photoresins by the real‐time photorheometry and analysis of their rheological parameters was carried out. Synthesized polymers exhibited high yield of insoluble fraction and thermal decomposition temperature at the weight loss of 10% above 300°C. Polymers AESO/IBOMA and AESO/THFMA showed the highest values of tensile modulus and tensile strength. Biodegradability of the synthesized polymers AESO/ME, AESO/THFA, and AESO/THFMA was investigated by measuring oxygen consumption in a closed respirometer. Such AESO‐based polymers can be a competitive solution to replace petroleum‐derived polymeric materials in additive manufacturing and reduce the environmental impact.

In this study, photocurable resins based on glycerol and vanillin were designed, synthesized, and applied to digital light processing three-dimensional (3D) printing and vitrimeric abilities such as shape-memory, self-healing, and recyclability have been investigated. First, photocurable resins were prepared and synthesized by combining renewable resources and photocuring as an environmentally friendly strategy for the synthesis of vitrimers. Afterward, the most suitable resin for optical 3D printing was selected by photorheometry, and the thermal and mechanical properties of the resulting polymers were tested. Furthermore, by activating dynamic transesterification reactions at elevated temperatures, the photocured polymer exhibited self-healing, recyclability, and shape-memory properties. The vitrimer with a weight ratio of 8:2 of glycerol- and vanillin-based monomers demonstrated a welding efficiency of tensile strength up to 114.12%, 75% recyclability by alcoholysis, and shape-memory properties above and below two glass transition temperatures.

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A novel dual cure photopolymerizable system was developed by combining two plant-derived acrylic monomers, acrylated epoxidized soybean oil and vanillin dimethacrylate, as well as the thiol monomer pentaerythritol tetrakis (3-mercaptopropionate). Carefully selected resin composition allowed the researchers to overcome earlier stability/premature polymerization problems and to obtain stable (up to six months at 4 °C) and selectively-polymerizable resin. The resin demonstrated rapid photocuring without an induction period and reached a rigidity of 317.66 MPa, which was more than 20 times higher than that of the other vanillin-based polymers. Improved mechanical properties and thermal stability of the resulting cross-linked photopolymer were obtained compared to similar homo- and copolymers: Young’s modulus reached 4753 MPa, the compression modulus reached 1634 MPa, and the temperature of 10% weight loss was 373 °C. The developed photocurable system was successfully applied in stereolithography and characterized with femtosecond pulsed two-beam initiation threshold measurement for the first time. The polymerization threshold of the investigated polymer was determined to be controlled by the sample temperature, making the footprint of the workstations cheaper, faster, and more reliable.