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

Abstract

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 (T_g ), 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 (T_g ≈ 61 °C) provide a 5.3 times higher impact strength than BDA, which is explained by the unique network homogeneity of thiol-yne photopolymers.

Keywords: double quantum solid state NMR; network formation; photopolymers; thiol-yne.