Toluene diisocyanate (TDI) reacts with 2-hydroxyethyl acrylate (KEA) during the synthesis of some urethane acrylate oligomers. The present work, deals with kinetic studies of the uncatalyzed bulk reaction of TDI with this monoalcohol. Back-titration and H-1-NMR in combination with HPLC are used to follow the reaction and allow a complete description of the system. The global reaction rate as well as those of each individual isocyanate group are well described by a second-order equation. Kinetic constants were calculated using the software SIMULBATCH(R). The rates of the different isocyanate groups, which characterize their selectivity, are compared and the model developed in the present study allows for a good prediction of the product structure and a better control of the polymerization process and the end-use properties as well. (C) 2000 John Wiley & Sons, Inc.