Brown Lauren A, Anderson W Curtis, Mitchell Nolan E, Gmernicki Kevin R, Long Brian K
Department of Chemistry, University of Tennessee, Knoxville, TN 37996, USA.
Polymers (Basel). 2018 Jan 2;10(1):41. doi: 10.3390/polym10010041.
Catalysts that employ late transition-metals, namely Ni and Pd, have been extensively studied for olefin polymerizations, co-polymerizations, and for the synthesis of advanced polymeric structures, such as block co-polymers. Unfortunately, many of these catalysts often exhibit poor thermal stability and/or non-living polymerization behavior that limits their ability to access tailored polymer structures. Due to this, the development of catalysts that display controlled/living behavior at elevated temperatures is vital. In this manuscript, we describe a Ni α-diimine complex that is capable of polymerizing ethylene in a living manner at temperatures as high as 75 °C, which is one of the highest temperatures reported for the living polymerization of ethylene by a late transition metal-based catalyst. Furthermore, we will demonstrate that this catalyst's living behavior is not dependent on the presence of monomer, and that it can be exploited to access polyethylene-based block co-polymers.
使用晚期过渡金属（即镍和钯）的催化剂已被广泛研究用于烯烃聚合、共聚以及合成高级聚合物结构，如嵌段共聚物。不幸的是，这些催化剂中的许多往往表现出较差的热稳定性和/或非活性聚合行为，这限制了它们获得定制聚合物结构的能力。因此，开发在高温下表现出可控/活性行为的催化剂至关重要。在本论文中，我们描述了一种镍α-二亚胺配合物，它能够在高达75°C的温度下以活性方式聚合乙烯，这是基于晚期过渡金属催化剂进行乙烯活性聚合所报道的最高温度之一。此外，我们将证明这种催化剂的活性行为不依赖于单体的存在，并且可以利用它来制备基于聚乙烯的嵌段共聚物。
