Applications of the study of end-groups. A new approach to the determination of transfer constants

A summary is given of established procedures depending on analyses of polymers for initiator fragments incorporated as end-groups; attention is paid to determinations of kinetic chain lengths and rates of initiation in polymerizations and also of the relative importances of combination and disproportionation during termination. Recent developments allow determination of transfer constants from information on the average number of initiator fragments in a molecule of a polymer, even in some cases where the transfer is degradative. Their applications are discussed for various transfer agents including iodoform and derivatives of propene from which allylic radicals could be produced. There is consideration of the possibilities of applying analyses for initiator fragments to study of transfer initiator, transfer to polymer and primary radical transfer.