Quantum-chemical investigation of the mechanism of ionic polymerization in crystals

Abstract

The results of quantum-chemical investigations of radiation-induced polymerization in molecular crystals are presented. The detailed calculations of the potentials energy curves characterizing the chain generation and propagation reactions, with explicit account of the reacting system interaction with the crystalline environment, provide a reasonable interpretation of the experimental observations. The basic conclusion is that the addition of the growing polymer ion to the monomer molecule placed at a lattice point needs no activation energy. The polymer chain is spontaneously moving in the interlayer space of the crystalline lattice at every propagation step, the overall displacement reaching a macroscopic value. Several termination mechanisms are briefly discussed. The possibility of molecular tunneling cannot be completely eliminated, however, it is expected to occur at the nonchemical preliminary stage of the reaction. © 1981.