The propagation kinetics of ethyl methacrylate (EMA) and ethyl a-hydroxy methacrylate (EHMA) has been subject to a computational study to understand their free radical polymerization (FRP) behavior in bulk and in solution using Density Functional Theory (DFT). The propagation of EHMA is studied in ethanol and toluene to assess the effect of hydrogen-bonding solvents on FRP of monomers with alpha-hydroxy functionality. Although EMA and EHMA resemble each other in structure, EHMA propagates faster in bulk due to the presence of intermolecular hydrogen-bonds, which tend to facilitate the approach of the propagating species. This falls in contrast with the experimentally observed lower propagation rates of EHMA in ethanol compared to toluene. Calculations show that the 2.28 rate acceleration in toluene is governed by the ratio of the pre-exponential factors, which reflect the entropies of activation, in both media. The polar protic solvent ethanol has a disruptive effect via hydrogen-bonding on the 6-membered ring shape of EHMA monomers thus decreasing the entropy of activation of the reaction. In the case of toluene, there are no special interactions with the hydrophobic solvent, the entropy of activation is higher than in ethanol. (C) 2012 Elsevier Ltd. All rights reserved.