Abstract
Polybutadiene‐ol was synthesized by solution radical polymerization of 1,3‐butadiene in the presence of hydrogen peroxide as initiator and 2‐propanol as solvent. The ratio of initiator to monomer molar concentration, [I~0~]/[M~0~], was varied while temperature, reaction time and the type and amount of solvent were kept constant. The effects on the M~n~; M~w~; M~v~; PDI, OH‐number and functionality of the synthesized polyols were studied. By taking several samples during a polymerization batch and analyzing them, the time of reaction was chosen as 100 min, after which the PDI changed dramatically. M~n~ decreased exponentially with increasing [I~0~]/[M~0~] according to the relationship M~n~ = 565.55 ([I~0~]/[M~0~])^−0.7553^. The decrease observed in M~w~ gradually levelled off with increasing [I~0~]/[M~0~] and molecular weight distribution broadened at larger values of [I~0~]/[M~0~]. The OH‐number increases with [I~0~]/[M~0~]. In addition to the number‐average molecular weight, functionality is dependent on the number of hydroxyl‐terminated chain radicals in the reaction medium. Copyright © 2003 Society of Chemical Industry