Studies in some new initiator systems for vinyl polymerization. II. Ammonia–halogen system as the redox initiator

The ammonia–halogen redox system has proved a promising initiator for polymerizing a number of vinyl monomers in aqueous media. Chlorine and bromine are most efficient, whereas iodine fails to initiate polymerization, probably due to its inhibitive tendency. Endgroups are halogen and amine and total about 0.5 per chain. On the basis of results of endgroup analysis, a mechanism of initiation through halogen and amine radicals, mainly through hydrogen atoms, is suggested. Consistent with the proposed mechanism the endgroup profile changes significantly with changes in pH.