Three-Dimensional Printing Fully Biobased Heat-Resistant Photoactive Acrylates from Aliphatic Biomass

Fabricating biobased heat-resistant photoactive acrylates from aliphatic biomass for three-dimensional (3D) printing is a great challenge with enormous implications for energy saving and sustainable development of polymers. Herein, two fully biobased acrylate monomers with di- or tri-functionality (BHMP2 and BHMP3) are synthesized from renewable glycidyl methacrylate and succinic acid or itaconic acid through a one-step method under solvent-free condition. These monomers are then cured by digital light processing 3D printing without diluters. The influences of structure on the curing behavior and performances are systematically studied. The BHMP3 resin shows excellent thermal and mechanical properties. Specifically, its glass transition temperature and heat deflection temperature under 0.455 MPa reach up to 183 and over 250 °C, respectively, while its tensile strength, modulus, and hardness are as high as 45.2 MPa, 4480 MPa, and 0.49 GPa, respectively. The outstanding performances of BHMP3 resin result from its compact cross-linking structures. This work pioneers a sustainable way to produce heat-resistant photoactive acrylates from renewable low-cost aliphatic biomass for photocurable 3D printing.