Multi-Functional Hybrid Terpolymer Thermosets Based on Thiols Bio-Based Epoxy and Benzoxazine Monomers

Hybrid thermosetting terpolymers based on epoxidized linseed oil (ELO), eugenol-based benzoxazine monomer (EPB), and thiols (2SH and 3SH) were synthesized and studied by focusing on the effects of the thiol-bearing functionality over the final performances. The curing dynamics were monitored by differential scanning calorimetry (DSC) and Fourier transform infrared spectrometry (FTIR). FTIR results showed that the curing process takes place in multiple steps and depends on the concentration of thiol used as a crosslinker. At the same time, the complexity of the reactions that take place within each system was highlighted by the curing profiles from DSC. Dynamic mechanical analysis (DMA) and nanoindentation data revealed that the mechanical features of the terpolymers can be modulated to achieve high stiffness, as in the case where 2SH and 3SH thiols were used in 0.25 wt.% or increased flexibility where 1% thiol concentrations were employed. Higher crosslinking density for hybrid terpolymers in comparison with the epoxy/benzoxazine sample indicated a good compatibility between the monomers and the crosslinking agents and the formation of additional chemical bonds within the networks. The ternary samples demonstrated good thermal stability (up to 300 °C) and high residual mass (>25%), which make them suitable candidates as flame-resistant coatings.