A MOLECULAR-ORBITAL STUDY OF THE DIMERIZATION PROCESS OF VINYL MONOMERS

Molecular orbital calculations were carried out for the dimerization s tep in the polymerization process of vinyl acetate and styrene through free radicals and ionic mechanisms. The calculations were performed f or monomers, dimers, their positive and negative ions, and free radica ls. The minimum-energy geometry is achieved in all cases, the geometri cal and electronic parameters are analyzed, a dimerization reaction pa thway is proposed, and the heats of polymerization obtained are in exc ellent agreement with experimental data. (C) 1997 John Wiley & Sons, I nc.