Mercaptan-induced polymerization and copolymerization reactions are intimately related to one type of olefin-mercaptan addition reaction, and may be interpreted or profitably studied only on the basis of a fundamental understanding thereof. Although such addition reactions may be classified into at least two basically different types, those relevant to the present discussion are free-radical chain reactions yielding products of anti-Markovnikov configuration (1,2).Chain reactions of the kind specified may be said to involve three essential steps. The first is the generation from the mercaptan (RSH), by any one of a variety of possible means, of mercaptyl (RS•) free radicals. An applicable method and the one most commonly employed, involves the attack of an oxidant (Ox) upon the mercaptan (Equation 1). The second step consists in the additive reaction of a mercaptyl free radical with an olefin molecule (Equation 2). The third step completes the addition through interaction of the derived free radical formed in the second step and a molecule of mercaptan, at the same time regenerating the chain-initiating mercaptyl free radical (Equation 3).1. RSH + Ox-> OxH + RS• 2. R'CH=CH2 + RS• ->R'(RSCH2)CH•

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