非均相条件下以BPO为引发剂的苯乙烯储备原子转移自由基聚合反应

Shenmin Zhu, Wenxin Wang, Wenping Tu, Deyue Yan
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引用次数: 17

摘要

通过一种新的聚合方法,成功地实现了苯乙烯在常规自由基引发剂(过氧化苯甲酰,BPO)存在下的反原子转移自由基聚合。体系先在70℃下反应10h,然后在110℃下聚合,自由基聚合控制良好,引发效率高,所得聚合物分子量分布窄,多分散性低至Mw/Mn = 1.32。BPO的引发机制与AIBN不同,因为自由基与CuII发生反应,BPO与CuI之间会发生氧化还原反应。通过实验数据推导了BPO/CuIICl2/bpy的起始机理。所得聚合物的分子量与根据上述机理计算的理论值一致。
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Reserse atom transfer radical polymerization of styrene using BPO as the initiator under heterogeneous conditions

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 Mw/Mn = 1.32. The initiation mechanism of BPO is different from that of AIBN because there is redox reaction between BPO and CuI generated from the reaction of radicals with CuII. The initiation mechanism of BPO/CuIICl2/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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