Computer simulation of alkyl (meth)acrylate associates

For esters of n-alkyl acrylate and n-alkyl methacrylate homologous series, the associative structures were modeled and the intermolecular interaction energy was determined by the method of molecular mechanics in the MM2 parameterization. It was shown that, starting with butyl esters, higher alkyl acrylates and alkyl methacrylates can form regular associates, where relative positions and orientations of ester molecules (their hydrocarbon fragments, ester groups, and double bonds) are ordered. These regular associated entities are identified with kinetically active associates, which were postulated previously in the model of associate intermediates for interpretation of some kinetic anomalies in radical polymerization of (meth)acrylates. In the acrylate and methacrylate homologous series, the intermolecular interaction energy increases with increasing size of the alkyl fragment of a molecule, thus favoring manifestation of the associates in the polymerization kinetics of higher alkyl (meth)acrylates.