Chemistry and kinetics of the chain transfer reaction

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Abstract
Chain transfer may be defined as a process in which the growing chain loses its capacity for further growth and the transfer agent (initiator, monomer, polymer, solvent or an extraneous compound) becomes capable of starting a new chain. This reaction has been subjected to extensive studies both for its relevance in interpreting the polymerization mechanism and for its practical importance as a method for controlling the molecular mass. In this communication the chemistry of the process is first described, then the classical kinetic approach based on the Mayo equation. Finally a selected number of recent results is discussed: the production of oligomers, the role of chain transfer in copolymerization, formation of branched polymers, catalyzed transfer and use of polyfunctional transfer agents.