Abstract
Reverse atom transfer radical polymerization of styrene in the presence of a conventional radical initiator (benzoylperoxide, BPO) in bulk was successfully implemented via a new polymerization procedure. The system first reacts at 70°C for ten hours, then polymerizes at 110°C, which results in a well-controlled radical polymerization with high initiation efficiency and narrow molecular weight distribution of the resulting polymer, i.e., the polydispersity is as low as M w /M n = 1.32. The initiation mechanism of BPO is different from that of AIBN because there is redox reaction between BPO and Cu I generated from the reaction of radicals with Cu II . The initiation mechanism of BPO/Cu II Cl 2 /bpy is deduced through the experimental data. The molecular weight of the resultant polymer is in agreement with the theoretical value calculated in accordance with the aforementioned mechanism.
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