Vegetable Oil-Based Resins Reinforced with Spruce Bark Powder and with Its Hydrochar Lignocellulosic Biomass

A bio-based polymeric matrix was developed by the copolymerization of a vegetable oil-based epoxy, epoxidized linseed oil (ELO), with dodecenyl succinic anhydride (DDSA). To obtain eco-friendly bio-composites, this matrix was combined with a natural filler: spruce bark powder (SB) with its hydrochar (HC) in various proportions ranged from 1 to 30 wt.%. The reactivities of these formulations were studied by DSC analysis that highlighted that both fillers have a high catalytic effect on the ELO–DDSA crosslinking reaction. The complementary studies by TGA, DMA, tensile tests, water absorption and Shore tests had shown that both HC and SB bring improvements to the mechanical properties of the composites, fulfilling multiple roles: (i) Both act as co-reactants in the copolymerization mechanism; (ii) HC acts as reinforcement, consolidating the network and providing stiffness and rigidity; and (iii) SB acts as plasticizer for reducing the brittle character of the epoxy resins.

Kinetic Analysis of the Curing Process of Biobased Epoxy Resin from Epoxidized Linseed Oil by Dynamic Differential Scanning Calorimetry

The curing process of epoxy resin based on epoxidized linseed oil (ELO) is studied using dynamic differential scanning calorimetry (DSC) in order to determine the kinetic triplet (Ea, f(α) and A) at different heating rates. The apparent activation energy, Ea, has been calculated by several differential and integral isoconversional methods, namely Kissinger, Friedman, Flynn–Wall–Ozawa (FWO), Kissinger–Akahira–Sunose (KAS) and Starink. All methods provide similar values of Ea (between 66 and 69 kJ/mol), and this shows independence versus the heating rate used. The epoxy resins crosslinking is characterized by a multi-step process. However, for the sake of the simplicity and to facilitate the understanding of the influence of the oxirane location on the curing kinetic, this can be assimilated to a single-step process. The reaction model has a high proportion of autocatalytic process, fulfilling that αM is between 0 and αp and αM < αp∞. Using as reference the model proposed by Šesták–Berggren, by obtaining two parameters (n and m) it is possible to obtain, on the one hand, the kinetic parameters and, on the other hand, a graphical comparison of the degree of conversion, α, versus temperature (T) at different heating rates with the average n and m values of this model. The good accuracy of the proposed model with regard to the actual values obtained by DSC gives consistency to the obtained parameters, thus suggesting the crosslinking of the ELO-based epoxy has apparent activation energies similar to other petroleum-derived epoxy resins.

Vegetable Oil-Based Thiol-Ene/Thiol-Epoxy Resins for Laser Direct Writing 3D Micro-/Nano-Lithography

The use of renewable sources for optical 3D printing instead of petroleum-based materials is increasingly growing. Combinations of photo- and thermal polymerization in dual curing processes can enhance the thermal and mechanical properties of the synthesized thermosets. Consequently, thiol-ene/thiol-epoxy polymers were obtained by combining UV and thermal curing of acrylated epoxidized soybean oil and epoxidized linseed oil with thiols, benzene-1,3-dithiol and pentaerythritol tetra(3-mercaptopropionate). Thiol-epoxy reaction was studied by calorimetry. The changes of rheological properties were examined during UV, thermal and dual curing to select the most suitable formulations for laser direct writing (LDW). The obtained polymers were characterized by dynamic-mechanical thermal analysis, thermogravimetry, and mechanical testing. The selected dual curable mixture was tested in LDW 3D lithography for validating its potential in optical micro- and nano-additive manufacturing. The obtained results demonstrated the suitability of epoxidized linseed oil as a biobased alternative to bisphenol A diglycidyl ether in thiol-epoxy thermal curing reactions. Dual cured thermosets showed higher rigidity, tensile strength, and Young’s modulus values compared with UV-cured thiol-ene polymers and the highest thermal stability from all prepared polymers. LDW results proved their suitability for high resolution 3D printing—individual features reaching an unprecedented 100 nm for plant-based materials. Finally, the biobased resin was tested for thermal post-treatment and 50% feature downscaling was achieved.

Yield and Selectivity Improvement in the Synthesis of Carbonated Linseed Oil by Catalytic Conversion of Carbon Dioxide

Carbonation of epoxidized linseed oil (CELO) containing five-membered cyclic carbonate (CC5) groups has been optimized to 95% by reacting epoxidized linseed oil (ELO) with carbon dioxide (CO2) and tetrabutylammonium bromide (TBAB) as catalysts. The effect of reaction variables (temperature, CO2 pressure, and catalyst concentration) on the reaction parameters (conversion, carbonation and selectivity) in an autoclave system was investigated. The reactions were monitored, and the products were characterized by Fourier Transform Infrared Spectroscopy (FT-IR), carbon-13 nuclear magnetic resonance (13C-NMR) and proton nuclear magnetic resonance (1H-NMR) spectroscopies. The results showed that when carrying out the reaction at high temperature (from 90 °C to 120 °C) and CO2 pressure (60–120 psi), the reaction’s conversion improves; however, the selectivity of the reaction decreases due to the promotion of side reactions. Regarding the catalyst, increasing the TBAB concentration from 2.0 to 5.0 w/w% favors selectivity. The presence of a secondary mechanism is based on the formation of a carboxylate ion, which was formed due to the interaction of CO2 with the catalyst and was demonstrated through 13C-NMR and FT-IR. The combination of these factors makes it possible to obtain the largest conversion (96%), carbonation (95%), and selectivity (99%) values reported until now, which are obtained at low temperature (90 °C), low pressure (60 psi) and high catalyst concentration (5.0% TBAB).