1,3-Diether-2-methacrylates with glycerol skeletons: tunable resins for stereolithography 3D printing

Abstract

The abundance of glycerol associated with biofuel production makes it an interesting substrate for a variety of new molecules. Our prior works have demonstrated the controlled and scalable synthesis of symmetric and asymmetric 1,3-diether-2-propanol compounds with a glycerol skeleton, which serve as versatile intermediates for further chemical modifications. Now we demonstrate that 1,3-diether-2-propanol compounds are useful building blocks to synthesize corresponding methacrylate monomers via Steglich esterification with methacrylic anhydride under mild catalytic conditions. The resulting methacrylate monomers were then successfully 3D printed as neat resins using a consumer-level printer. The thermal and mechanical properties of the printed materials were thoroughly investigated. The 3D-printed samples of 1,3-diethoxypropan-2-yl methacrylate (MAA-DEP) possessed good combinations of mechanical and thermal properties, with a tensile strength of 1.61 MPa, elongation at break of 143%, and a glass transition temperature (T_g) near 0 °C. A notable feature of the MAA-DEP monomer is its ability to dissolve polystyrene (PS). Thus, glycerol-based (meth)acrylate monomers present not only new molecules for 3D printing resins with tunable properties but also offer advancements in additive manufacturing by demonstrating how glycerol-derived acrylates also have solvating power to incorporate (waste) thermoplastics into SLA-printable formulations.