SYNOPSISThe radical polymerization of isoprene in alcohol solutions initiated by hydrogen peroxide was studied. It was found that alcohols were components of the initiated system and that their fragments with hydroxyl groups were included in every second molecule of an oligomer irrespective of the type of alcohol, of the monomer conversion, and of the oligomer molecular weight. The oligomer yields and its molecular weight were determined by alcohols through their effect upon the phase state of polymerization systems.

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The MWD and 14C distribution of poly(2-alkylbutadienes) obtained in the presence of bis-[( -crotyl-14C)nickel iodide] in benzene solution has been studied. It is shown that both the polymer chain length and the nature of the 2-alkyl substituent in polydiene play a decisive role in determining the dissociation degree of dimeric -allylic active sites. The correlation between MWD and the ratio of the monomeric species of active sites to the dimeric ones is established.