MODELING COPOLYMERIZATION KINETICS

The composition and rate behavior of free radical copolymerizations is usually described by the Mayo-Lewis (ML) model and the associated reactivity ratios, r1 and r2. Particularly with respect to rate, a number of systems have been found to be poorly described by the simple ML model and the penultimate unit effect (PUE) model has been suggested as an explanation. A small but significant amount of work has been done with small model analogues of polymer chains and with ESR which has established the chemical feasibility of a PUE. This paper reviews recent work with pulsed laser polymerization kinetic measurements which are successfully described in terms of a modified PUE. It is concluded that the strength of the PUE correlates inversely with the monomer reactivity ratio product, r1r2. The effect is important for rate, but not for composition.