No abstract

Vegetable oils were investigated as plasticizers to improve the sustainability of rubber compounding. The potential use of different vegetable oils as an alternative to petroleum‐based rubber process oils was reviewed. This article presents a literature review on the current understanding of the influence of vegetable oil properties on natural rubber (NR) compounding. Hansen solubility parameters of the vegetable oils were determined to assist with the selection of vegetable oil for NR. We believe that the use of Hansen parameters could make the use of vegetable oils in rubber more convenient and cost‐effective.

The kinetics of the epoxidation of castor oil in benzene with peracetic acid formed in situ from acetic acid and hydrogen peroxide in the presence of an ion-exchange resin as a catalyst was studied. Eighteen pseudo-two-phase models are established that, besides the main reactions of peracid and epoxy ring formation, also consider the side reaction of epoxy ring cleavage with acetic acid. Kinetic expressions for the heterogeneously catalyzed peracetic acid formation are developed on the basis of Eley–Rideal and Langmuir–Hinshelwood–Hougen–Watson postulates. An equation derived for the temperature dependency of the chemical equilibrium constant for peracetic acid formation is applied. Kinetic and adsorption parameters were estimated by fitting experimental data using the Marquardt method. The best-fit model correctly interprets data of double bond and epoxy group contents as a function of reactant ratios, catalyst concentrations, and temperatures applied during epoxidation. The proposed model better fits experimental data than the pseudohomogeneous model reported in the literature.

A kinetic model was proposed for the epoxidation of vegetable oils with peracetic acid formed in situ from acetic acid and hydrogen peroxide in the presence of an acidic ion exchange resin as a catalyst. The model is pseudo-homogeneous with respect to the catalyst. Besides the main reactions of peracetic acid and epoxy ring formation, the model takes into account the side reaction of epoxy ring opening with acetic acid. The partitioning of acetic acid and peracetic acid between the aqueous and organic phases and the change in the phases? volumes during the process were considered. The temperature dependency of the apparent reaction rate coefficients is described by a reparameterized Arrhenius equation. The constants in the proposed model were estimated by fitting the experimental data obtained for the epoxidations of soybean oil conducted under defined reaction conditions. The highest epoxy yield of 87.73% was obtained at 338 K when the mole ratio of oil unsaturation:acetic acid:hydrogen peroxide was 1:0.5:1.35 and when the amount of the catalyst Amberlite IR-120H was 4.04 wt.% of oil. Compared to the other reported pseudo-homogeneous models, the model proposed in this study better correlates the change of double bond and epoxy group contents during the epoxidation process. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. III45022]

The liquid-liquid equilibrium constant for acetic acid in a quinary system olive oil-epoxidized olive oil-acetic acid-hydrogen peroxide-water was experimentally determined for temperatures and component ratios relevant for in situ epoxidation of plant oils. The values have the constant range from 1.52 to 2.73. To predict the equilibrium constant for acetic acid, the experimental data were correlated with UNIQUAC (universal quasi chemical) and NRTL (non-random two liquid) activity coefficient models. For simplified calculation of the phase equilibrium the insolubility of olive oil and epoxidized olive oil in the water, as well as insolubility of water and hydrogen peroxide in the olive oil and epoxidized olive oil, was assumed. The root mean square deviation (RMSD) of the experimental and calculated values of the liquid-liquid equilibrium constant for acetic acid is 0.1910 for the UNIQUAC model and 0.1815 for the NRTL model. For rigorous flash calculation, when the partitioning of all components between the phases was assumed, the RMSD for the NRTL model is 0.1749.