Exploring Network Formation of Tough and Biocompatible Thiol‐yne Based Photopolymers

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This work deals with the in‐depth investigation of thiol‐yne based network formation and its effect on thermomechanical properties and impact strength. The results show that the bifunctional alkyne monomer di(but‐1‐yne‐4‐yl)carbonate (DBC) provides significantly lower cytotoxicity than the comparable acrylate, 1,4‐butanediol diacrylate (BDA). Real‐time near infrared photorheology measurements reveal that gel formation is shifted to higher conversions for DBC/thiol resins leading to lower shrinkage stress and higher overall monomer conversion than BDA. Glass transition temperature (Tg), shrinkage stress, as well as network density determined by double quantum solid state NMR, increase proportionally with the thiol functionality. Most importantly, highly cross‐linked DBC/dipentaerythritol hexa(3‐mercaptopropionate) networks (Tg ≈ 61 °C) provide a 5.3 times higher impact strength than BDA, which is explained by the unique network homogeneity of thiol‐yne photopolymers.