Living Polymerization of Bulky Aryl Isocyanide with Arylrhodium Complexes
Living Polymerization of Bulky Aryl Isocyanide with Arylrhodium Complexes
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DOI：
10.1021/om0509692
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发表时间：
2006-02
期刊：
影响因子：
2.8
通讯作者：
K. Onitsuka;Mari Yamamoto;Tomoko Mori;F. Takei;Shigetoshi Takahashi
中科院分区：
文献类型：
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作者：
K. Onitsuka;Mari Yamamoto;Tomoko Mori;F. Takei;Shigetoshi Takahashi
定义良好的芳铑配合物Rh(Ar)(nbd)(PPh3) (Ar = me2c6h3,2,4,6 - pri3c6h2, 2- phc6h4, 2- me -1-萘基，9-蒽基，C(Ph)CPh2；nbd = 2,5-降冰片二烯)由[Rh(nbd)Cl]2与LiAr和PPh3反应得到，有效地引发了PPh3存在下邻位具有大体积取代基的芳基异氰化物的活性聚合，得到了多分散性指数窄且产率高的聚异氰化物。Rh络合物上庞大的芳基对于获得高引发剂效率是必不可少的，而芳基异氰酸酯上庞大的取代基对于形成高分子量聚合物是必需的。动力学研究和嵌段共聚物的形成证实了该体系的活性。聚合速率不取决于单体的浓度，而取决于PPh3的浓度。
Well-defined arylrhodium complexes Rh(Ar)(nbd)(PPh3) (Ar = Me2C6H3, 2,4,6-Pri3C6H2, 2-PhC6H4, 2-Me-1-naphthyl, 9-anthracenyl, C(Ph)CPh2; nbd = 2,5-norbornadiene) that were prepared from the reaction of [Rh(nbd)Cl]2 with LiAr and PPh3 effectively initiated the living polymerization of aryl isocyanides possessing bulky substituents at the ortho position in the presence of PPh3 to give poly(isocyanide)s with narrow polydispersity indexes in good yields. The bulky aryl groups on the Rh complex were essential to achieving high initiator efficiency, whereas the bulky substituents on aryl isocyanides were required for the formation of high molecular weight polymers. The living nature of the present system was confirmed by kinetic studies as well as the formation of block copolymers. The polymerization rate was dependent not on the concentration of monomers, but on the concentration of PPh3.