A statistical modeling procedure is established for carbocation polymerization with the characteristics of living with chain transfer. A single state model is suggested for cases of narrow molecular weight distribution, whereas a multi-state model is claimed for cases of broad distribution. In the multi-state case, it is demonstrated how the overall kinetics can be derived using the expectations and variances of the kinetic parameters rather than those of individual states, thereby simplifying the modeling step. Although the expectation and variance do not follow the relationship of the Arrhenius equation, a procedure is given for how to account for temperature dependence. The proposed statistical method minimizes the number of parameters to identify and therefore is expected to help establish a model with fewer experiments. The whole procedure is demonstrated through an experimental study of isobutylene polymerization.
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