Sequential thiol click reactions: formation of ternary thiourethane/thiol-ene networks with enhanced thermal and mechanical properties.

We report the physical properties of thiol-ene networks modified with thiourethane or urethane linkages, either along the main chain or as a branched component in the network, respectively. Because of the robust and orthogonal nature of thiol-isocyanate and thiol-ene reactions, these networks can be formed in a two-step, one-pot synthesis. Resultant networks were characterized using dynamic mechanical analysis, mechanical testing and other complementary techniques. It was found that incorporating (thio)urethanes into the networks increased Tg, but also increased strain at break and toughness while decreasing cross-link density. The changes in physical properties are discussed in terms of a proposed dual network morphology. These facile modifications to thiol-ene networks demonstrate how molecular-level, nanoscale changes can have a profound influence on the macroscale properties through hierarchical development of network morphology.