METHYL OLEATE EPOXIDATION WITH TBHP CATALYZED BY VANADYL(IV) DIKETONATE AND VANADYL(IV) SALICYLIDENE 2-AMINOTEREPHTHALATE

• Main Author: Abdul Aziz, Rival
• Format: Theses
• Language: Indonesia
• Subjects: Kimia
• Online Access: https://digilib.itb.ac.id/gdl/view/65269
• Institution: Institut Teknologi Bandung

Epoxidized fatty acid methyl ester (EFAME) is a potential PVC plasticizer that may replace phthalate-based plasticizers. The general production of EFAME involves organic acids and hydrogen peroxide with a mole ratio exceeding the olefin. The reaction releases large heat in very short time. Epoxidation of FAME with tertiary butyl hydroperoxide (TBHP) catalyzed by transition metal-based catalyst showed a milder and safer reaction. The conversion of internal olefins into epoxides may be facilitated by oxophilic transition metals, such as vanadium, molybdenum, tungsten, and manganese at high valent. Herein, vanadyl(IV) acetylacetonate, VO(acac)2, and vanadyl(IV) salicylidene 2-aminoterephthalate, VO(HBDC-FISal)( H2O), were examined in the epoxidation of methyl oleate. The extended tightbinding (xTB) program implemented in ORCA 5.0.2 was used to study the epoxidation of methyl oleate theoretically. The study at GFN2-xTB level showed that the energy barrier, ?????‡(323 K), for the Sharpless mechanism was +104,8 kJ/mol and +124,3 kJ/mol in gas-phase and n-hexadecane, respectively. n- Hexadecane was used to mimic the electronic environment of the complex in methyl oleate. The interaction of VO(acac)2 with excess TBHP showed the formation of a vanadium(V) complex based on the visible light spectrum and qualitative magnetic measurements. Infrared spectrum of the isolated VO(acac)2 intermediate after the contact with 2 mol of TBHP showed a characteristic of oxide vanadium. Vanadium phenoxyimine of VO(HBDC-FI-Sal)(H2O) was likely obtained in the one-pot reaction of HBDC-FI-Sal ligand and VO(acac)2. The formation of the complex was observed by IR spectroscopy, measurement of magnetic properties, and gravimetric analysis. Epoxidized methyl oleate (EMO) was achieved at the highest yield when 0.3 mol% of VO(acac)2 and 3 mol eq of TBHP were employed in the reaction at 50 °C for 7 h. Complexes of VO(acac)2, VO(bzbz)2, and VO(HBDC-FI-Sal)(H2O) showed catalytic activity of EMO formation at 58%, 55%, and 62%, respectively