Shuqi Dong, Ling Cai, Ziying Han, Bo Liu* and Dongmei Cui*,
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引用次数: 0
Abstract
Direct coordination copolymerization of polar monomers with olefin should be the most atom- and energy-efficient strategy to prepare functional polyolefins, which encounters challenges to trade-off the activity and polar monomer incorporation and molecular weight of the afforded product. Herein, we report that using the fluorenyl-modified N-heterocyclic carbene-ligated scandium complex, the copolymerization of ethylene with N-(phenyl)-cis-5-norbornene-endo-2,3-dimethylene (NPh) was achieved with high activity (2580 kg·molSc–1·h–1) and high incorporation of NPh (31.6%). The investigation of several amine-substituted polar monomers indicated that the high activity and incorporation ability were attributed to the moderate steric and weak basicity of the amine group, which not only ensure the coordination priority of NPh but also facilitate its swift swing from the Sc–σ–N chelation mode to the Sc–π–C═C polymerization mode illustrated by density functional theory (DFT) calculation. This established a new polar group self-assisted mechanism, which will give inspirations to tackle the challenging issue in the copolymerization of olefin with polar monomers.
期刊介绍:
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.