Epoxidized methyl oleate

G. Lligadas, J. C. Ronda, M. Galia, U. Biermann, J. O. Metzer, Synthesis and characterization of polyurethanes from epoxidized methyl oleate based polyether polyols as renewable resources, J. Pol. Sci. Part A Pol. Chem. 44 (2005) 634. 

Nicolau A, Martignago Mariath R, Agostini Martini E, dos Santos Martini D, Samios D.The polymerization products of epoxidized oleic acid and epoxidized methyl oleate with cis-l,2-cyclohexanedicarboxylic anhydride and triethylamine as the initiator chemical structures, thermal and electrical properties. Mater Sci Eng C 2010 30 951-962. 

Doll, K.M., Erhan, S.Z., 2006. Synthesis and performance of surfactants based on epoxidized methyl oleate and glycerol. J. Surfact. Deterg. 9, 377-383. 

The ability of titanium-grafted silicas in catalyzing the epoxidation with TBHP of fatty compounds was first tested on two pure Qg monounsaturated FAMEs methyl oleate (ds-9-octadecenoate Scheme 12.1) and methyl elaidate (trans-9-octadecenoate) [49]. In both cases, selectivity to 9,10-epoxystearate was very high (>95%) and the reaction was fully stereospecific, confirming that epoxidation with titanium catalysts and TBHP proceeds via a non-radical mechanism with retention of configuration at the C=C bond. Ti-MCM-41 was more active than Ti-SiC>2 (Fig. 12.1). Actually, methyl oleate was almost completely converted after... 

Table 12.1 Catalytic performances in the epoxidation of methyl oleate (cis) and methyl elaidate (trans). (Adapted from [49]).

Ferulic acid, a phenolic acid that can be found in rapeseed cake, has been used in the synthesis of monomers for ADMET homo- and copolymerization with fatty acid-based a,co-dienes [139]. Homopolymerizations were performed in the presence of several ruthenium-based olefin metathesis catalysts (1 mol% and 80°C), although only C5, the Zhan catalyst, and catalyst M5i of the company Umicore were able to produce oligomers with Tgs around 7°C. The comonomers were prepared by epoxidation of methyl oleate and erucate followed by simultaneous ring opening and transesterification with allyl alcohol. Best results for the copolymerizations were obtained with the erucic acid-derived monomer, reaching a crystalline polymer (Tm — 24.9°C) with molecular weight over 13 kDa. 

The use of isolated fatty acids as substrates for epoxidations has already been reported in 1990 with the epoxidation of methyl oleate and methyl linoleate by MT0/H202 in ferf-butanol. After respectively 24 and 2 h, good yields of either the corresponding diol (methyl oleate) or the monoepoxide (methyl linoleate) are obtained (respectively 92% and 80%) [48]. Under biphasic conditions, the MTO-catalyzed epoxidation of methyl linoleate yields a mixture of mono- and diepoxide (approximately 1 1) at complete conversion after 6 h [79]. Finally, a conjugated methyl linoleate is treated with the MT0/H202 system in biphasic conditions, but here, poor results are obtained after 24 h at room temperature, yielding 26% of the 11,12-monoepoxide and 20% of the 9,10-epoxide [80]. 

The number of metal zeolites and their application to the epoxidation of olefins rose in parallel from the late 1980s. TS-2, Ti,Al-P, Ti-P, Ti-MWW and, rarely, Ti-MOR are catalysts that have been studied in some detail [7-9, 35, 77-84]. TS-2 behaves, according to the few studies published, similarly to TS-1. The greater spaciousness of pores in Ti-Beta zeolites and of external cups in Ti-MWW allows the epoxidation, under mild conditions, of olefins unable to diffuse in TS-1 and TS-2, such as methylcyclohexenes, cyclododecene, norbornene, camphene and methyl oleate [80-83]. Steric constraints still prevail over electronic factors, however, as in medium pore Ti-zeolites, even in the epoxidation of linear olefins (Table 18.9). It is generally believed that active sites and epoxidation mechanisms are not significantly different from those of TS-1. 

Similar oxidants are used for epoxidation of esters of unsaturated carboxylic acids. Methyl oleate is oxidized with peroxybenzoic acid [295] or peroxylauric acid [174] to methyl 9,10-epoxystearate acid in respective yields of 67 and 76%. Alkaline 50% hydrogen peroxide in methanolic solution transforms diethyl ethylidenemalonate at pH 8.5-9.0 and at 35-40 C over a period of 1 h into ethyl 2-ethoxycarbonyl-2,3-epoxybutyrate in 82% yield [145], A somewhat exotic oxidizing agent, dimethyldioxirane, converts ethyl tra/u-cinnamate into ethyl 2,3-epoxyhydrocinnamate in 63% isolated yield [210]. 

Fatty acid epoxides have numerous uses. In particular, oils and fats of vegetable and animal origin represent the greatest proportion of current consumption of renewable raw materials in the chemical industry, providing applications that cannot be met by petrochemicals [64]. Polyether polyols produced from methyl oleate by the Prileshajev epoxidation (using peracetic acid) are an example. Epoxidized soybean oil (ESBO) is a mixture of the glycerol esters of epoxidized linoleic, linolenic, and oleic acids. It is used as a plasticizer and stabilizer for poly (vinyl chloride) (PVC) [1] and as a stabilizer for PVC resins to improve flexibility, elasticity, and toughness [65]. The ESBO market is second to that of epoxy resins and its world wide production... 

Schmitz, W.R. J.G. Wallace. Epoxidation of methyl oleate with hydrogen peroxide. /. Am. Oil Chem. Soc. 1954,31, 363-365. 

Kimura and co-workers reported the first iron-catalyzed olefin epoxidation with H2O2 as oxidant and Fe(acac)3 as the catalyst (89). The oxidation of cis- and troras-stilbene afforded troras-epoxide as the major product with a product yield of 96%. Similar stereochemical features were observed in the epoxidation of other substrates, such as methyl oleate and cis- or trons-9-octadecen-l-ol (89). 

A. Kockritz, M. Blumenstein and A. Martin, Epoxidation of methyl oleate with molecular oxygen in the presence of aldehydes , Eur J Lipid Sci Technol, 2008, 110,581-6. 

The vapor-pheise photochemical reaction of chlorine dioxide with ethylene was observed by Furst (65) to give chloroacetic acid. Leopold and Mutton (137) discovered that the reaction between triolein and chlorine dioxide is accelerated by light cind gives a mixture of products, containing carbonyl, hydroj l, euid epoxide groups, as well as chlorine. CSilorine dioxide oxidations carried out by Lindgren and co-workers on cyclohexene (143) and methyl oleate (142) in the cib-sence of special illumination showed only a little... 

Epoxidized soybean oil, butyl ester Epoxidized soybean oil, methyl ester Ethyl oleate Glutaric anhydride Glyceryl dilaurate Glyceryl tripropionate n-Heptadecanol 2,2, 4,4, 5,5 -Hexachlorobiphenyl Hexamethylene glycol Hexyl alcohol Hexyl benzoate Hydrogen peroxide 12-Hydroxystearyl alcohol Isoamyl alcohol... 

As with oleate and linoleate, some volatile decomposition compounds are formed from linolenate hydroperoxides that cannot be explained by the classical A and B cleavage mechanisms, including acetaldehyde, butanal, 2-butyl furan, methyl heptanoate, 4,5-epoxyhepta-2-enal, methyl nonanoate, methyl 8-oxooctanoate, and methyl lO-oxo-8-decenoate. Some of these minor volatile oxidation products can be attributed to further oxidation of unsaturated aldehydes. Other factors contribute to the complexity of volatile products formed from hydroperoxides, including temperature of oxidation, metal catalysts, stability of volatile products and competing secondary reactions including dimerization, cyclization, epoxidation and dihydroperoxidation (Section E). 

---