CGC-Scandium-Mediated Copolymerization of Ethylene with Amine-Functionalized Cyclic Olefins

IF 13.1 1区 化学 Q1 CHEMISTRY, PHYSICAL
Shuqi Dong, Ling Cai, Ziying Han, Bo Liu* and Dongmei Cui*, 
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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.

Abstract Image

CGC 钪介导的乙烯与胺官能环烯烃的共聚作用
极性单体与烯烃的直接配位共聚应该是制备功能性聚烯烃的最节省原子和能源的策略,但在活性与极性单体掺入量和所得产物的分子量之间进行权衡却面临挑战。在此,我们报告了利用芴基修饰的 N-杂环碳烯配位钪络合物,实现了乙烯与 N-(苯基)-顺-5-降冰片烯-内向-2,3-二甲苯(NPh)的共聚,具有高活性(2580 kg-molSc-1-h-1)和高 NPh 结合率(31.6%)。对几种胺取代的极性单体的研究表明,高活性和高掺杂能力得益于胺基团适度的立体性和弱碱性,这不仅保证了 NPh 的配位优先性,而且通过密度泛函理论(DFT)计算,促进了 NPh 从 Sc-σ-N 螯合模式迅速转变为 Sc-π-C═C 聚合模式。这建立了一种新的极性基团自辅助机理,为解决烯烃与极性单体共聚的难题提供了启示。
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来源期刊
ACS Catalysis
ACS Catalysis CHEMISTRY, PHYSICAL-
CiteScore
20.80
自引率
6.20%
发文量
1253
审稿时长
1.5 months
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.
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