The initiation of styrene polymerization with n‐butyllithium in toluene was investigated spectrophotometrically. The rate of the first step of initiation is first order in both monomer and catalyst, and the activation energy is 26.3 kJ · mol−1. The kinetic analysis revealed a number of kinetic transitions attributed to the formation of secondary aggregates from reacted and unreacted n‐C4H9Li. The molecular weight distribution narrows with increasing reaction temperature, indicating the activation energy of the last step of initiation to be higher than that of propagation.
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