Acrylates have gained importance because of their ease of conversion to high-molecular-weight polymers and their broad industrial use. Methyl methacrylate (MMA) is a well-known monomer for free radical polymerization, but its a-methyl substituent restricts the chemical modification of the monomer and therefore the properties of the resulting polymer. The presence of a heteroatom in the methyl group is known to increase the polymerizability of MMA. Methyl alpha-hydroxymethylacrylate (MHMA), methyl alpha-methoxymethylacrylate (MC(1)MA), methyl alpha-acetoxymethylacrylate (MAcMA) show even better conversions to high-molecular-weight polymers than NIMA. In contrast, the polymerization rate is known to decrease as the methyl group is replaced by ethyl in ethyl a-hydroxymethylacrylate (EHMA) and t-butyl in t-butyl alpha-hydroxymethylacrylate (TBHMA). In this study, quantum mechanical tools (B3LYP/6-31G*) have been used in order to understand the mechanistic behavior of the free radical polymerization reactions of acrylates. The polymerization rates of MMA, MHMA, MC(1)MA, MAcMA, EHMA, TBHMA, MC(1)AN (alpha-methoxymethyl acrylonitrile), and MC(1)AA (alpha-methoxymethyl acrylic acid) have been evaluated and rationalized. Simple monomers such as allyl alcohol (AA) and allyl chloride (AC) have also been modeled for comparative purposes. (c) 2005 Wiley Periodicals, Inc.