THE THERMOCHEMISTRY OF RADICAL POLYMERIZATIONS IN THE GAS-PHASE - A THEORETICAL CONTRIBUTION

In this paper, we propose a simple model to predict the thermochemistr y of free radical polymerizations in the gas phase. It consists of ass uming that the heat of polymerization of a monomer A=B is equal to the enthalpy change of the process HABAH + A=B --> HABABAH. The heat of f ormation of species HABAH, A=B and HABABAH not yet experimentally dete rmined are theoretically calculated using various ab initio methods of quantum chemistry. The enthalpies of polymerization of a series of mo nomers could be calculated in this way. They are generally in good agr eement with the corresponding available experimental data. They could be also rationalized in terms of the stabilization energies of the mon omers and the growing chains.