The project presented herein takes advantage of the expertise of our research group in click chemistry and dual-cure systems to approach different technological challenges in an efficient and innovative way. The problems we aim to solve in this project are as follows: poor mechanical properties of 3D printed materials, excessive heat accumulation in electronic devices, lack of stimuli-sensitive materials for reversible thermomechanical actuators, inability to reprocess thermoset materials and the generation of permanent residues. The general objective is the preparation and characterization of novel thermosets obtained via click reactions and optimization of their use in the aforementioned applications. Click reactions are fast, efficient and selective, therefore facilitate dual-cure processes where products with desired properties are obtained in a controlled and sequential way, especially when latent catalysts are used. It is proposed to use the following reactions, most of which are of click nature: thiol-ene, thiol-epoxy, thiol-isocyanate, epoxy-amine, Michael additions and homopolymerizations of acrylic and epoxy derivatives. The design, preparation and characterization of thermosets with thermoadaptive topologies will be realized through poly(thiourethane) networks obtained by click thiol-isocyanate condensation using a thiol excess so that poly(thiourethane) network reorganization takes place at high temperatures. For functional applications such as actuators in soft robotics, we will design and characterize reconfigurable hybrid systems starting from multilayer shape memory materials with different thermal and mechanical properties (thermosets, liquid crystalline elastomers and vitrimers) and by applying the dual-cure strategy to improve the assembly. This will allow us to design sequential and controlled actuation mechanisms in one single device and to improve significantly its mechanical strength. The quality of pieces manufactured layer-by-layer will be enhanced by dual-cure technology. In 3D printing, by adding a thermal initiator and a second reactive component to UV-curable formulations, and by a post-curing step after printing, it will be possible to improve final properties, homogeneity and controllability of cure. Using a fused deposition modeling equipment, conveniently adapted, actuators with shape memory properties for complex geometries will be fabricated . By 1D/2D simulation and subsequent experimental validation, and by the novel incorporation of dual-curability for better control of reaction, the processing of composite materials will be optimized. For the preparation of dielectric layers with high conductivity for electronics, materials will be developed using poly(ether) o poly(thioether) matrices reinforced with boron nitride, or in some cases, carbon nanotubes. The Lewis acid-base interactions between the matrices and boron nitride will facilitate the anchorage between the reinforcing additive and the matrix, thereby improving thermal conductivity.