The study of oxazolidone formation from 9,10‐epoxyoctadecane and phenylisocyanate

Abstract

The formation of oxazolidone from 9,10-epoxyoctadecane and phenylisocyanate was studied. One branch of epoxidized vegetable oil with one epoxy group per chain corresponds to 9,10-epoxyoctadecane. This model could explain the probability of oxazolidone formation from natural oil-derived epoxides. Epoxidized natural oils are TG consisting of glycerin and three FA with or without one to three epoxy groups in the middle of the chain. To study oxazolidone formation from an internal epoxy group without possible interference from the side reactions on the ester group, 9,10-epoxyoctadecane was selected as the most appropriate model compound. Epoxy groups in the middle of a long aliphatic chain are of low reactivity toward isocyanates, and preparation of oxazolidones requires fairly harsh conditions such as high temperatures and catalysts, which also promote side reactions. The dominant side reaction is rearrangement of the epoxy groups. We found that the direction and magnitude of the rearrangement and the yield of any particular product depended on the catalyst used. Lithium chloride, aluminum trichloride, and zinc iodide catalyzed oxazolidone formation, along with the catalysis of side reactions such as ketone and carbonate formation. Aluminum trichloride showed the highest conversion of 9,10-epoxyoctadecane to oxazolidone. Aluminum triisopropoxide, triphenylantimony iodide, and imidazole did not catalyze the formation of oxazolidone. They were effective as catalysts of epoxy group rearrangement and promoted the formation of hydroxyl, ketone, and carbonate compounds. Hydroxyl groups reacted with isocyanate to produce urethane.Paper no. J10256 in JAOCS 80, 595-600 (June 2003).FIG. 1. FTIR spectra of the liquid product synthesized with zinc iodide, lithium chloride, and aluminum trichloride as catalysts.

Rigid Polyurethane Foam Production from Palm Oil‐Based Epoxidized Diethanolamides

“…Fourier Transform Infra Red analysis was used to examine the functional groups present in the polyurethane foam. The carbonyl group of the oxazolidone ring appeared gradually from foam 9 to foam 0 at around 1,750 cm -1 [18] (Fig. 4).…”

“…But in foam 10, produced by diethanolamides synthesized by RBDPKO o only, the carbonyl group of oxazolidone was not detected. In the study of the reaction between aromatic isocyanate and a fatty epoxide, where the epoxy groups were in the middle of the chain, AlCl 3 Lewis acid is the most efficient converter of oxazolidone when compared with other catalysts, namely lithium chloride and zinc iodide [18]. In view of these results, we selected AlCl 3 -THF complex as catalyst so that the thermally stable oxazolidone can be introduced into the polyurethane backbones.…”

“…Yeganeh et al reported that the introduction of oxazolidones to the polyurethane backbone from reacting glycidol with isocyanate-terminated polyurethane prepolymers improved the thermal and the stress-strain properties of the elastomers [17]. Although the epoxy groups in the middle of the fatty acid chain of triacylglycerides have lower reactivity towards isocyanate, Javni et al found that the yield of oxazolidones is actually dependent on the type of catalyst used [18].…”

Synthesis of Palm Oil‐Based Diethanolamides

“…Many different types of catalysts in the reaction between 9, 10-epoxyoctadecane and phenylisocyanate to form oxazolidone have been Scheme 1 Reaction scheme of the synthesization of diethanolamide. R 1, R 2 , R 3 are the alkyl chains with or without epoxide(s) functionality [16]. Other study reported on improved compressive strength of epoxy modified polyurethane rigid foams by reacting epoxy resin, isocyanate, and additives at 80°C for 24 h [17].…”

The Effect of Reaction Temperature on Retaining Oxirane Oxygen Contents in the Synthesis of Epoxidized Diethanolamides

“…Yaganeh and co-workers reported that the introduction of oxazolidones to polyurethane backbone from reacting glycidol with isocyanate-terminated polyurethane prepolymers improved the thermal and the stress-strain properties of the elastomers [12] . Although the epoxy groups in the middle of the fatty acid chain of triacylglycerides have lower reactivity towards isocyanate, Javni and co-workers found that the yield of oxazolidones is actually dependent on the type of catalyst used [13] .…”