Volumetric 3D-printing of Thiol-Ene crosslinkable Poly(ε-Caprolactone) Quinten Thijssen 1 , Astrid Quaak 1 , Joseph Toombs 2 , Elly De Vlieghere 1 , Laurens Parmentier 1 , Hayden Taylor 2 , Sandra Van Vlierberghe 1 1 Ghent University, Polymer Chemistry and Biomaterials Group, Belgium, 2 University of California, Design for Emerging and Nanoscale Manufacturing Group, USA We developed photo-crosslinkable poly(ε-caprolactone) (PCL) networks through orthogonal thiol-ene chemistry and applied them in volumetric 3D-printing. 1 The step-growth polymerized networks are tunable, predictable by means of the rubber elasticity theory and it is shown that their mechanical properties are significantly improved over their acrylate crosslinked counterparts. Tunability is introduced to the materials, by altering Mc (or the molar mass between crosslinks), and its effect on the thermal properties, mechanical strength and degradability of the materials is evaluated. Moreover, excellent volumetric printability is illustrated and we report the smallest features obtained via volumetric 3D-printing to date, for thiol-ene systems. Finally, by means of in-vitro and in-vivo characterization of 3D-printed constructs, we illustrate that the volumetrically 3D-printed materials are biocompatible. This combination of mechanical stability, tunability, biocompatibility and rapid fabrication by volumetric 3D-printing charts a new path towards bedside manufacturing of biodegradable patient-specific implants. References 1. Thijssen, Q.; Quaak, A.; Toombs, J.; Vlieghere, E. De; Parmentier, L.; Taylor, H.; Vlierberghe, S. Van. Volumetric Printing of Thiol-Ene Photo-Cross-Linkable Poly(ε-Caprolactone): A Tunable Material Platform Serving Biomedical Applications. Adv. Mater. 2023 , 2210136. https://doi.org/10.1002/ADMA.202210136.
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