The reaction order with respect to TiCl 4 was investigated in the living polymerization of isobutylene (IB) initiated by 2-chloro-2,4,4-trimethylpentane (TMPCl)/TiCl 4 in hexane/methyl chloride (Hx/MeCl) 60/40 v/v cosolvents at −80 °C. It was found that the reaction is more complex than previously believed. The TiCl 4 order was found to be closer to 1 at [TMPCl] 0 > [TiCl 4 ] 0, and closer to 2 when [TMPCl] 0 < [TiCl 4 ] 0 . Kinetic complexity is demonstrated by the fraction order in TiCl 4, and the rate-acceleration found when [TMPCl] 0 ≫ [TiCl 4 ] 0 . A comprehensive mechanistic scheme to explain the kinetic behavior of living IB polymerizations is proposed. Further, a new fiber optic mid-IR monitoring method for more convenient kinetic investigations is demonstrated.
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Puskás et al. (1998) studied this question.
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