The proposed synthesis strategy can be started with the crude SO, which will be epoxidized to produce ESO (an industrially available product). The ESO will be employed to produce thermosetting epoxy materials with aromatic networks, and non-isocyanate polyurethane (NIPU) networks. Aromatic-containing ESO-based thermosets can be engineered for production of biocomposites, adhesives, or surface coatings. NIPU networks are suggested to be produced via fixation of CO2 through a cyclo carbonation reaction, followed by amine curing, and can be interchangeably employed, wherever polyurethane is used.

Phase 1: Fabrication of soybean-based thermosetting epoxy materials, with aromatic networks (Synthesis, Characterizing, Fabrication of the biocomposites, and Evaluation of the mechanical properties).
Phase 2: Synthesis and characterization of the non-isocyanate polyurethane (NIPU) networks.

Successful outcome of this project will result in the fabrication of a two novel resins, based on SO with a high market value. Both phases would have a significant novelty, which guarantee the publication of the results in the prestigious journals, after submitting invention disclosures. The process has been designed with scale-up considerations to be easily applicable. The outcome of this project would be the cornerstone of our future plans for more collaborative projects between different parties, working on the functionalized resins. The results of this study will be disseminated through webpage development, newsletters, publishing articles and presentations in various national and international conferences.

Updated October 30, 2022:
In this quarter, we tested two different most promising deep-eutectic solvents such as acetyl choline and oxalic acid (DES02), and acetyl choline and butyric acid (ESO-DES06) by following washing and without washing steps. From this work we confirmed that acetyl choline and oxalic acid (DES02) catalyst was the best to optimize soybean oil for epoxidation. We found that choline chloride –oxalic acid (DES02) catalyst effectively epoxidized soybean oil throughout sharing electron mechanism during epoxidation. During the characterization of these bio resins we observed the following results:
1. Conventional epoxidized soybean oil (CESO)-based films exhibited higher redness color index compared to the films developed with DES-02 (Choline chloride-oxalic acid) and DES-06 (Choline chloride-butyric acid) catalysts, indicating an increase in epoxidation occurred due to catalysts.
2. Significant amount of oxirene (oxygen) was absorbed by an unsaturated fatty acids of soybean oil to be converted in saturated fatty acids during epoxidation when DES-02 (Choline chloride-oxalic acid) and DES-06 (Choline chloride-butyric acid) catalysts were added by following washing steps.
3. A lower pH content was observed in epoxidized soybean oil (ESO) samples when soybean oil was epoxidized with DES-02 (Choline chloride-oxalic acid) and DES-06 (Choline chloride-butyric acid) catalysts.
4. We observed a decrease in iodine values and increase in carbon double bond conversions when soybean oil was epoxidized with DES-02 (Choline chloride-oxalic acid) catalysts. In addition, higher epoxy yields were obtained when soybean oil was epoxidized by DES-02 (Choline chloride-oxalic acid) catalysts.
5. During rheological studies, a lower viscosity in epoxidized soybean oils (ESOs) when soybean oil was epoxidized with DES-02 (Choline chloride-oxalic acid) catalysts was observed. In addition an increase in thermal stability of 350 C of all epoxy resins were observed.
6. During FTIR characterization the results confirmed that the functional groups like C-H, N-H, C-C, CHO and C-H evolved during the epoxidations.
7. 1HNMR experiments confirmed that soybean oil was fully epoxidized when DES-02 (Choline chloride-oxalic acid) catalysts were employed during epoxidations.

In the next quarter, synthesis of product 2 to product 3 will be attempted and subsequent curing to obtain non-isocyanate polyurethane network from product 3 will be the target.

Updated January 24, 2023:
The aim of this research is to develop low-cost value-added bio-based epoxy resins from conventional soybean oils and commercialize the technology to be scaled up for epoxy resin production for chemical industries. In this quarter, the epoxidized soybean oil (ESO) was developed through the synthesis of conventional soybean oil by applying deep eutectic solvent catalysts, such as choline chloride-oxalic acid (DES-02) and choline chloride-butyric acid (DES-06) followed by a three step washing neutralization process. The impact of catalysts on the epoxidized process was verified using titration methods, infrared (IR) spectroscopy and nuclear magnetic resonance (NMR). The results demonstrated that an optimal carbon-carbon double bond conversion with the high selectivity of 90 % were obtained when soybean oil was epoxidized with bi-functional DES-02 catalysts. Meanwhile, the conventional epoxidized soybean oil (CESO) synthesis in absence of any deep eutectic catalysts yielded relatively low carbon-carbon double bond conversions with 30% selectivity. Various novel bio-based epoxy resins with equal amounts of ESO and acrylic acid, as a monomer, were developed followed by injection moldings. The developed epoxidized soybean resin films were characterized with dynamic mechanical analysis (DMA) and thermomechanical analysis (TMA). The results showed that resin films catalyzed by DES-02 and DES-06 led to an improvement in storage modulus (ca. 2000 MPa) and loss modulus (Ca. 390 MPa).

Updated April 25, 2023:
In this quarter, we primarily focused on publishing a peer reviewed international journal article from the Epoxidized soybean oil (ESO) study. The ESO was developed through the synthesis of conventional soybean oil by applying deep eutectic solvent catalysts, such as choline chloride–oxalic acid (DES-02) and choline chloride–butyric acid (DES-06) followed by three steps of washing neutralization processes. The impact of the catalysts on the epoxidation process was verified using titration methods in combination with infrared and nuclear magnetic resonance spectroscopies. The results showed an optimal carbon–carbon double bond conversion with a high selectivity of 73% when soybean oil was epoxidized with bifunctional DES-02 catalysts. The conventional epoxidized soybean oil synthesis without deep eutectic catalysts yielded relatively low carbon–carbon double bond conversions with 5% selectivity. Various novel bio-based epoxy resins with equal amounts of ESO and acrylic acid as monomers were developed, followed by injection molding. Bio-based epoxidized soybean resin films were characterized by dynamic mechanical and thermomechanical analyses. The results showed that resin films catalyzed by DES-02 and DES-06 improved the storage modulus (ca. 2000 MPa) and loss modulus (ca. 390 MPa).

Updated July 27, 2023:
In this quarter, we developed halloysite nanotubes (HNTs)-based thermoset resins. For this process, 20 g of epoxidized soybean oil (ESO) and acrylic acid was poured into a 50 ml beaker and 0.05, 0.1 and 0.2 g of HNTs were added to each beaker. Then 4 g of the mixture were poured into silicon molds (5 cm×2 cm), and they were covered by a glass plate and placed gently in an oven preheated to 90°C. In addition, we developed methanol treated high thermoset bio-resin film. First, methanol-treated-cellulose nanofiber (MCNF) was prepared by following water exchange method. Afterward, MCNF was added to previously developed ESO and sonicated for 15 mins. Then, acrylic acid and 3% 4-dimethylaminopyridine (DMAP) were added and further stirred for 15 mins. The resulting solution was then molded (5 cm × 2 cm), and cured at 110 °C for 2, 4 and 6 h. Some of the advantages are shorter film formulation time (~ 2 h), higher tensile force is required to break the film (~700 N) and high thermal stability (~395 °C).

We tested two different most promising deep-eutectic solvents such as acetyl choline and oxalic acid (DES02), and acetyl choline and butyric acid (ESO-DES06) by following washing and without washing steps. From this work we confirmed that acetyl choline and oxalic acid (DES02) catalyst was the best to optimize soybean oil for epoxidation. We found that choline chloride –oxalic acid (DES02) catalyst effectively epoxidized soybean oil throughout sharing electron mechanism during epoxidation. The results showed that resin films catalyzed by DES-02 and DES-06 led to an improvement in storage modulus (ca. 2000 MPa) and loss modulus (Ca. 390 MPa). Further, the results showed an optimal carbon–carbon double bond conversion with a high selectivity of 73% when soybean oil was epoxidized with bifunctional DES-02 catalysts. The conventional epoxidized soybean oil synthesis without deep eutectic catalysts yielded relatively low carbon–carbon double bond conversions with 5% selectivity.

Global price of SO is estimated to be in range of US $0.6-0.7 per liter, whereas for Epoxidized oil, this is in range of US $1.2-2 per liter, up to 3 folds higher. The global price of vinyl epoxy resins, the epoxy resin with better properties, would be even higher, in range of US $2-3 per liter. A leap from these so called “first-generation” value-added products into the second-generation products, results in more profits: 1 liter of polyurethane resin is estimated to be traded up to 10 USD. These prices have been estimated based on the average prices provided by the current Chinese vendors- accessed www.alibaba.com, 2019. Moreover, in this proposal, the future scale-up of the processes was considered carefully. Therefore, the use of complex technologies, expensive solvents, toxic organometallic catalysts, problematic reactants, and expensive separation-purification steps have been avoided. The technology required for the synthesis of these resin is of conventional type- used for well-known poly-condensation and radical polymerization processes with minor modifications. It is simple, safe, and works under the ambient conditions, and can be readily employed, even at decentralized chemical factories. Our decent estimate for the budget required for stablishing a small-size plant (i.e., at the farm) with the production capacity of 60,000 kg per year- which can work during the winter time, or when there would be no cultivations or farming-1 shift, would be no more than US $500,000. If a net benefit margin of just $ 2.5 per liter of the resin is considered, the annual benefit exceeds US $150,000 per year.