Department of Chemistry, University of Louisiana at Lafayette, Lafayette, LA 70504, USA.
Chem Commun (Camb). 2021 Apr 7;57(27):3331-3334. doi: 10.1039/d1cc00682g. Epub 2021 Mar 4.
Simultaneous atom transfer radical polymerization (ATRP) and nitroxide radical coupling (NRC) seems impossible because the presence of nitroxide radicals would quench the radical polymerization immediately. However, by combining a nitroxide radical and an ATRP active halogen, a halogen group that can initiate one polymer chain by ATRP, into one functional reagent and adding this functional reagent to an ATRP system, concurrent ATRP-NRC relay polymerization was carried out successfully under proper reaction conditions. The key to success was the conjugate radical trapping and re-initiation took place repeatedly, resulting in polymers with inserted alkoxyamine linkages. This novel relay polymerization method provides numerous possibilities for macromolecular architecture/functionality tailoring by using of different functional reagents.
同时原子转移自由基聚合（ATRP）和氮氧自由基偶联（NRC）似乎是不可能的，因为氮氧自由基的存在会立即猝灭自由基聚合。然而，通过将氮氧自由基和 ATRP 活性卤原子（一种可以通过 ATRP 引发一条聚合物链的卤原子）结合到一个功能试剂中，并将该功能试剂添加到 ATRP 体系中，在适当的反应条件下成功地进行了并发的 ATRP-NRC 接力聚合。成功的关键是共轭自由基的反复捕获和再引发，导致聚合物中插入了烷氧基胺键。这种新型的接力聚合方法为通过使用不同的功能试剂来调整大分子结构/功能提供了许多可能性。
