Biobased Composites by Photoinduced Polymerization of Cardanol Methacrylate with Microfibrillated Cellulose

Biobased monomers and green processes are key to producing sustainable materials. Cardanol, an aromatic compound obtained from cashew nut shells, may be conveniently functionalized, e.g., with epoxy or (meth)acrylate groups, to replace petroleum-based monomers. Photoinduced polymerization is recognized as a sustainable process, less energy intensive than thermal curing; however, cardanol-based UV-cured polymers have relatively low thermomechanical properties, making them mostly suitable as reactive diluents or in non-structural applications such as coatings. It is therefore convenient to combine them with biobased reinforcements, such as microfibrillated cellulose (MFC), to obtain composites with good mechanical properties. In this work a cardanol-based methacrylate monomer was photopolymerized in the presence of MFC to yield self-standing, flexible, and relatively transparent films with high thermal stability. The polymerization process was completed within few minutes even in the presence of filler, and the cellulosic filler was not affected by the photopolymerization process.

Evaluation of Reactive Diluent Impact on Stability of Systems Viscosity in UV-Curable Compositions

This study investigated the impact of various reactive diluents on viscosity of uncured mixture at 50 °C over a 12-week period. This criterion is important to predict the shelf life of uncured composition. Studied mono-functional acrylate monomers were: hydroxypropyl methacrylate (HPMA), hydroxyethyl methacrylate (HEMA), tetrahydrofurfuryl acrylate (THFA), isobornyl methacrylate (IBOMA), isobornyl acrylate (IBOA), 2-(2-Ethoxyethoxy)ethyl acrylate (EOEOEA), acryloyl morpholine (ACMO), glacial methacrylic acid (GMAA) and phosphate acrylate monomer (PAM); and various solvents: isopropanol(IP) ethyl acetate (EA), butyl acetate (BA). There was found the difference of effect on the systems viscosity in time between the mono-functional monomers and solvents. HPMA and IPA showed the most stable viscosity values in time.

UV-Light Curing of 3D Printing Inks from Vegetable Oils for Stereolithography

Typical resins for UV-assisted additive manufacturing (AM) are prepared from petroleum-based materials and therefore do not contribute to the growing AM industry trend of converting to sustainable bio-based materials. To satisfy society and industry’s demand for sustainability, renewable feedstocks must be explored; unfortunately, there are not many options that are applicable to photopolymerization. Nevertheless, some vegetable oils can be modified to be suitable for UV-assisted AM technologies. In this work, extended study, through FTIR and photorheology measurements, of the UV-curing of epoxidized acrylate from soybean oil (AESO)-based formulations has been performed to better understand the photopolymerization process. The study demonstrates that the addition of appropriate functional comonomers like trimethylolpropane triacrylate (TMPTA) and the adjusting of the concentration of photoinitiator from 1% to 7% decrease the needed UV-irradiation time by up to 25%. Under optimized conditions, the optimal curing time was about 4 s, leading to a double bond conversion rate (DBC%) up to 80% and higher crosslinking density determined by the Flory–Rehner empirical approach. Thermal and mechanical properties were also investigated via TGA and DMA measurements that showed significant improvements of mechanical performances for all formulations. The properties were improved further upon the addition of the reactive diluents. After the thorough investigations, the prepared vegetable oil-based resin ink formulations containing reactive diluents were deemed suitable inks for UV-assisted AM, giving their appropriate viscosity. The validation was done by printing different objects with complex structures using a laser based stereolithography apparatus (SLA) printer.