Polymerization kinetics and functional group conversions were determined by Fourier transform infrared spectroscopy (FTIR). Cured resin mechanical properties were evaluated using a three-point flexural test, carried out with a hydraulic universal test system. Polymerization shrinkage stress was measured with a tensometer coupled with simultaneous real-time conversion monitoring.
The incorporation of thiol–ene mixtures as reactive diluents into conventional dimethacrylate resins previously was shown to combine synergistically advantageous methacrylate mechanical properties with the improved polymerization kinetics and reduced shrinkage stress of thiol–ene systems. In these systems, due to thiol consumption resultant from both the thiol–ene reaction and chain transfer involving the methacrylate polymerization, the optimum thiol:ene stoichiometry deviates from the traditional 1:1 ratio. Increasing the thiol:ene stoichiometry up to 3:1 results in systems with equivalent flexural modulus, 6–20 % reduced flexural strength, and 5–33 % reduced shrinkage stress relative to 1:1 stoichiometric thiol:ene systems.
Due to their improved overall functional group conversion, and shrinkage stress reduction while maintaining equivalent flexural modulus, methacrylate–thiol–ene resins, particularly those with excess thiol, beyond the conventional 1:1 thiol:ene molar ratio, yield superior dental restorative materials compared with purely dimethacrylate resins.