Influence of reactive diluent composition on properties and bio-based content of itaconic acid-based additive manufacturing materials

Among the additive manufacturing techniques, UV-curing processes are of special interest, as they allow for the fabrication of thermosetting materials with high resolutions and optical clarity. Traditionally, these processes require the use of formulations, consisting of polyester or polyurethane oligomers, combined with photoinitiators and reactive diluents. The latter are usually vinyl monomers such as acrylates or acrylamides, used to reduce the viscosity of the formulation and render it processable by additive manufacturing machines. In this work, we investigate whether a combination of diluents can be used to tune the thermomechanical properties of the printed materials, and if it can be exploited to increase their overall bio-based content without compromising their performance. To do so, a series of itaconic acidbased polyesters with diferent chemical structures (aliphatic–aromatic) were synthesized and formulated with reactive diluents acryloyl morpholine (ACMO) and isobornyl acrylate (IBOA). The physicochemical properties of the prepared formulations, together with their reactivity towards UV-light were assessed via photo diferential scanning calorimetry (photo-DSC) and photo-rheology measurements. The same formulations were then used to fabricate test specimen via digital light processing (DLP) 3D printing, which were characterized on their thermomechanical properties by means of dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA) measurements. The glass transition temperature of the printed samples reached a maximum of 98 °C, while the diluent ratio could be used to manipulate the Tg in a linear trend. All materials of this study exhibited Td,5% above 250 °C, suggesting good thermal stability. These results show that materials with a very high bio-based content (up to 85%) and very promising thermomechanical properties could be obtained by employing a diluent mixture during the formulation phase.