The Prediction of Reactivity in Radical Polymerisation

The essential reactions in radical polymerisation involve the addition of a radical to a molecule. In the propagation process, the radical is typically a polymer and the molecule is a monomer in transfer, the molecule is a transfer agent and, in initiation, the radical is a species of low molar mass. It is now possible to predict the reactivity of both the radicals and the molecules by means of a revised form of the Patterns Scheme, and a review is presented here of the historical development of the state of understanding of reactivity in the various component steps in a polymerisation process propagated by radicals.