The reactivity of initiator radicals V. The application of the revised patterns scheme

Recently, the interpretation of the reactivity of polymer radicals has been developed by means of some improvements to the so-called Patterns Scheme, itself an advance over the Alfrey-Price Q-e Scheme. Using the reactivity of a radical with styrene as a measure of its 'general' (i.e. thermodynamic) reactivity, it has been shown that a parameter denoting radical polarity can easily be deduced from polymerisation data, and that these 2 parameters can be used quantitatively to characterise the behaviour of that radical in copolymerisations in general. It thus becomes possible to forecast monomer reactivity ratios with much greater precision than heretofore. The present article extends this treatment to the reactions of initiator radicals with monomers.; Recently, the interpretation of the reactivity of polymer radicals has been developed by means of some improvements to the so-called Patterns Scheme, itself an advance over the Alfrey-Price Q-e Scheme. Using the reactivity of a radical with styrene as a measure of its 'general' (i.e. thermodynamic) reactivity, it has been shown that a parameter denoting radical polarity can easily be deduced from polymerisation data, and that these 2 parameters can be used quantitatively to characterise the behaviour of that radical in copolymerisations in general. It thus becomes possible to forecast monomer reactivity ratios with much greater precision than heretofore. The present article extends this treatment to the reactions of initiator radicals with monomers.