ABSTRACT Kinetics of curing of maleated castor oil glycerides with styrene was studied by differential scanning calorimetry and rheology. The resin was synthesized from biodiesel‐derived crude glycerol. Curing rates were fitted to several empirical models (autocatalytic model, Kamal's model and a model with vitrification). The three models showed a good fitting with experimental data at conversions lower than 0.55 for temperatures ranging from 30 to 50°C. However, the model that includes vitrification showed a better fitting in the entire range of conversions and the same temperatures. At higher temperatures (50–60°C), some deviations were observed for the three models at low and high conversions. Gel times were obtained from rheological studies and the apparent activation energies were calculated thereof. Gel times were 300–2700 s. The values of apparent activation energy obtained for this castor oil‐based copolymer (47.2–52.3 kJ/mol) were within range of commercial unsaturated polyester resins. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132 , 41344.