QUANTUM-CHEMICAL INTERPRETATION OF ELECTRON-DONOR EFFECTS ON THE REACTIVITY OF ANIONIC ACTIVE-CENTERS OF POLAR MONOMERS IN NONPOLAR MEDIA

The method of modified neglect of differential overlap (MNDO) was used to evaluate the relative energy preference of the interaction of meth yllithium with vinyl and polar groups of acrylonitrile and methyl acry late in both the presence and the absence of an electron donor (ethyle nediamine). According to calculations, in the case of methyl acrylate, in contrast to that of acrylonitrile, the presence of the electron do nor makes the addition of methyllithium to the polar group (deactivati on of the initiator) more preferable than the addition of this group t o the vinyl group (polymerization initiation). The results of calculat ions are compared with experimental data on the anionic polymerization of monomers under discussion.