Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, State Key Laboratory of Structural Chemistry, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 Yangqiao Road West, Fuzhou, 350002, People's Republic of China.
University of Chinese Academy of Sciences, Beijing, 100049, People's Republic of China.
ACS Macro Lett. 2022 Mar 15;11(3):354-361. doi: 10.1021/acsmacrolett.2c00010. Epub 2022 Feb 24.
The developments of the living alkene polymerization method have achieved great progress and enabled the precise synthesis of important polyalkenes with controlled molecular weight, molecular weight distribution, and architecture through an anionic, cationic or radical strategy. However, it is still challenging to develop a living alkene polymerization method through an all-in-one strategy where anionic and radical characteristics are merged into one polymerization species. Here, a versatile living polymerization method is reported by introducing a well-established all-in-one covalent-anionic-radical Barbier strategy into a living polymerization. Through this living covalent-anionic-radical Barbier polymerization (Barbier CARP), narrow distributed polystyrenes, with as low as 1.05, are successfully prepared under mild conditions with a full monomer conversion by using wide varieties of organohalides, for example, alkyl, benzyl, allyl, and phenyl halides, as initiators with Mg in one pot. This living covalent-anionic-radical polymerization via a Barbier strategy expands the methodology library of polymer chemistry and enables living polymerization with an unconventional polymerization mode.
活烯聚合方法的发展取得了重大进展，通过阴离子、阳离子或自由基策略，能够精确合成具有受控分子量、分子量分布和结构的重要聚烯烃。然而，通过将阴离子和自由基特性合并到一个聚合物种中开发出一种全合一的活烯聚合方法仍然具有挑战性。在这里，通过将成熟的全合一共价阴离子自由基巴尔比耶策略引入到活聚中，报道了一种通用的活聚合方法。通过这种活的共价阴离子自由基巴尔比耶聚合（Barbier CARP），在温和条件下，使用广泛的各种有机卤化物（例如烷基、苄基、烯丙基和苯基卤化物）作为引发剂，在一个锅中使用 Mg，成功制备了窄分布的聚苯乙烯， 低至 1.05，并且单体转化率完全。这种通过巴尔比耶策略的活的共价阴离子自由基聚合扩展了聚合物化学的方法库，并能够以非常规的聚合模式进行活聚合。
