Biocompatible PVAc-g-PLLA Acrylate Polymers for DLP 3D Printing with Tunable Mechanical Properties

The technological advancement of Additive Manufacturing has enabled the fabrication of various customized artifacts and devices, which has prompted a huge demand for multimaterials that can cater to stringent mechanical, chemical, and other functional property requirements. Photocurable formulations that are widely used for Digital Light Processing (DLP)/Stereolithography (SLA) 3D printing applications are now expected to meet these new challenges of hard and soft or stretchable structural requirements in addition to good resolution in multiple scales. Here we present a biocompatible photocurable resin formulation with tunable mechanical properties that can produce hard or stretchable elastomeric 3D printed materials in a graded manner. Acrylate poly(lactic acid) (PLA) grafted polyvinyl acetate (PVAc) polymer was mixed with hydroxyl ethyl methacrylate (HEMA) and hydroxyl ethyl acrylate (HEA) as reactive diluents (50-70 wt %) in various compositions to form a series of photocurable resin formulations. Depending on the nature of the reactive diluent (HEMA or HEA) and their weight percentage, the mechanical properties of the 3D printed parts could be fine-tuned from hard (Tensile strength 20.6 ± 2 MPa, elongation 2 ± 1%) to soft (Tensile strength 1.1 ± 0.2 MPa, elongation 62 ± 8%) materials. The printed materials displayed remarkable dye absorption (95%), showing stimuli-responsive behavior for dye release (with respect to both pH and enzyme), while also demonstrating high cell viability (>90%) for mouse embryonic (WT-MEF) cells and degradability in PBS solution. These biobased 3D printing resins have the potential for a variety of applications, including tissue engineering, soft robotics, dye absorption, and elastomeric actuators.