Isoprene Polymerization by Butyllithium in Cyclohexane. I. Initiation Reaction

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Abstract
Kinetic studies, using a gas chromatographic method, of the consumption of n-, sec-, and t-butyllithium during the polymerization of isoprene in cyclohexane show in the three cases a sigmoidal curve. When the concentration of polyisoprenyllithium increases, the initiation rate goes through a maximum with n-butyllithium but continuously increases in the two other cases. The three corresponding lithium-butoxides have a drastic effect on the initiation rate. Thus, the addition of n-butoxide strongly increases the initial rate, but the rate further decreases except in the case of sec-butyl-lithium. The behavior of the sec-butoxide is roughly the same, but more limited, while the t-butoxide causes a slight initial promotion in the case of n-BuLi and sec-BuLi but decreases the initiation rate in the case of t-BuLi. These results are discussed in terms of association of organolithium molecules and ion pairs reactivity.