Studies of Radical Alternating Copolymerization. I. Quantitative Determination of the Relative Reactivities between Free Comonomers and a Complex between Them; A Theoretical Treatment in Terms of Frontier Molecular Orbital Interactions. Application to Radical Maleic Anhydride-Vinyl Acetate Alternating Copolymerization |
| |
| Authors: | Roger Arnaud Claude Caze Jacques Fossey |
| |
| Institution: | 1. Laboratoire de chimie générale , Université Scientifique et Médicale de Grenoble , F38041, Grenoble, France;2. Laboratoire de chimie macromoléculaire , Université de Sciences et Techniques de Lille , F59655, Villeneuve D′Ascq, France;3. CNRS , F94320, Thiais, France |
| |
| Abstract: | A simple quantitative determination of the ratio β1 of rate constants kij corresponding to the addition of a complex or a free monomer on a same growing chain in alternating copolymerization was determined. The application of this method to the case of alternating maleic anhydride (A)-vinyl acetate (D) copolymerization give for β1 = kAC/kAD and for β2 = kDC/kDA (C refers to the complex) the respective values of 7 and 0. A complex was more reactive than A but less reactive than D toward a growing chain. In order to explain these reactivities, a frontier molecular orbital treatment was proposed. A good qualitative correlation with experimental results was obtained. |
| |
| Keywords: | |
|
|
