A new dual-curing system based on sequential thiol–epoxy click polycondensation and epoxy anionic homopolymerization was studied. Formulations of diglycidyl ether of bisphenol A and trimethylolpropane tris(3-mercaptopropionate) with 1-methylimidazole as a base catalyst and excess of epoxy groups were prepared and characterized. The curing process is sequential: fast thiol–epoxy polycondensation takes place first, followed by slower homopolymerization of excess epoxy groups. This makes it possible to define curing sequences with easy time–temperature control for both curing stages. The network build-up process during the first curing stage can be easily modelled assuming ideal polycondensation, which allows tailoring the structure and properties of the intermediate materials. The homopolymerization of the excess epoxy groups in the second curing stage results in a higher glass transition temperature (T_g) in comparison with the stoichiometric thiol–epoxy material, thus extending the application of thiol–epoxy thermosets to wider temperature ranges.

Acrylate chemistry has found widespread use in dual-curing systems over the years. Acrylates are cheap, easily handled and versatile monomers that can undergo facile chain-wise or step-wise polymerization reactions that are mostly of the “click” nature. Their dual-curing processes yield two distinct and temporally stable sets of material properties at each curing stage, thereby allowing process flexibility. The review begins with an introduction to acrylate-based click chemistries behind dual-curing systems and relevant reaction mechanisms. It then provides an overview of reaction combinations that can be encountered in these systems. It finishes with a survey of recent and breakthrough research in acrylate dual-curing materials for shape memory polymers, optical materials, photolithography, protective coatings, structured surface topologies, and holographic materials.