Resin catalyzed alcoholysis of epoxidized fatty esters: Effect of the alcohol and the resin structures

The effects of different alcohol molecular configurations and resin structures were analyzed on the acid-resin catalyzed addition of alcohols to epoxidized fatty esters. Emphasis was placed on the addition of alpha- and beta-branched alcohols. Regarding the catalysts, the effect of the acid strength as well as that of the diffusion constraints on the reaction rate and products distributions, was determined. Reaction rate increases with the acid strength but the selectivity shows the opposite trend when highly branched alcohols are added. Epoxide ring-opening rate decreases by increasing the number of branches and size of the alcohol. Branches in alpha position introduce a higher steric hindrance than branches in beta position. Low resin crosslinkage and/or high external surface area are necessary conditions to activate the epoxide when polystyrene-based resins are used as catalysts. The obtained by-products were the ketone, from epoxide rearrangement reaction, and transesterified products. when reaction times were relatively long. (c) 2005 Elsevier B.V. All rights reserved.