A novel triglyceride containing alpha,beta-unsaturated ketone was prepared through photoperoxidation from high oleic sunflower oil by two steps one pot environmentally friendly procedure. This new enone-containing triglyceride was crosslinked with diaminodiphenylmethane (DDM) via aza-Michael addition. A kinetic study of the reaction of p-toluidine with either enone-containing methyl oleate or epoxidized methyl oleate, as model compounds, allowed us to establish the higher reactivity of the former, thus confirming this curing system as an alternative to amine-cured epoxidized vegetable oils. The thermal properties of thermosets from enone- and epoxy-containing triglycerides with DDM have been evaluated. (c) 2008 Wiley Periodicals, Inc.