Abstract
The development of high-performance transition metal catalysts has long been a major driving force in academic and industrial polyolefin research. Late transition metal-based olefin polymerization catalysts possess many unique properties, such as the ability to generate variously branched polyolefins using only ethylene as the feedstock and the capability of incorporating polar functionalized comonomers without protecting agents. Here we report the synthesis and (co)polymerization studies of a simple but extremely versatile α-imino-ketone nickel system. This type of catalyst is easy to synthesize and modify, and it is thermally stable and highly active during ethylene polymerization without the addition of any cocatalysts. Despite the sterically open nature, these catalysts can generate branched Ultra-High-Molecular-Weight polyethylene and copolymerize ethylene with a series of polar comonomers. The versatility of this platform has been further demonstrated through the synthesis of a dinuclear nickel catalyst and the installation of an anchor for catalyst heterogenization.
Highlights
The development of high-performance transition metal catalysts has long been a major driving force in academic and industrial polyolefin research
Ni(II)-based catalysts have been reported with the ability to generate high molecular weight polyolefins
Our preliminary studies showed that the combination of α-diimine or pyridine-imine ligands with the pre-generated cationic nickel center ([Ni(allyl)]+) is highly active in ethylene polymerization
Summary
The development of high-performance transition metal catalysts has long been a major driving force in academic and industrial polyolefin research. Late transition metal-based olefin polymerization catalysts possess many unique properties, such as the ability to generate variously branched polyolefins using only ethylene as the feedstock and the capability of incorporating polar functionalized comonomers without protecting agents. We report the synthesis and (co)polymerization studies of a simple but extremely versatile α-iminoketone nickel system. Despite the sterically open nature, these catalysts can generate branched UltraHigh-Molecular-Weight polyethylene and copolymerize ethylene with a series of polar comonomers. The versatility of this platform has been further demonstrated through the synthesis of a dinuclear nickel catalyst and the installation of an anchor for catalyst heterogenization. Brookhart’s seminal works in 1995 showed that α-diimine nickel catalysts (Fig. 1, I)
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