Quantum chemical simulation of homopolycondensation of aromatic o-ketocarboxylic acid pseudochloroanhydrides

Abstract

Within the supermolecule theory, the intermolecular interaction of a monomer, a catalyst, and a solvent involved in the polycondensation of aromatic o-ketocarboxylic acid pseudochloroanhydrides is simulated. A transition state is found in the dimerization reaction of the simplest representative of the class of 3-chloro-3-phenylphthalylidene monomers under study. It is established that a solvent molecule (nitrobenzene) can coordinate through the functional chlorine atom of 3-chloro-3-phenylphthalylidene, thus hindering the formation of the active center, and hence, the growth of the polymeric chain. As a rule, in the presence of nitrobenzene the activation energy of the dimerization reaction of 3-chloro-3-phenylphthalylidene slightly lowers as compared to that in the gas phase.