Abstract
With the help of a self-invented microflow reactor containing a spiral tubular, the kinetics of the anionic bulk polymerization of styrene initiated by n-butyllithium and t-butyllithium at the different temperatures were investigated. The results confirmed that hexameric-aggregated n-butyllithium could initiate the polymerization of St and form the supramolecular structure of polystyryllithium at first. Then, the polymer coils could block the diffusion of the monomers into the ion-pairs and result in a stationary-conversion platform (SCP). The supramolecular would be disaggregated due to the energy accumulation. The higher the polymerization temperature is, the shorter SCP will be. The results also indicated a larger aggregation based on hexameric-aggregated n-butyllithiums existed. The results of AFM revealed that the diameter of such supramolecular aggregations ranged from 20–30 nm and 50–60 nm. Moreover, the structure of initiator aggregations, which had great effect on the initiating rate, was determined by the molecular structure of the initiator. Therefore, the findings could explain the wide difference in anionic polymerization rate using difference lithium initiators.
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