Synthesis, Characterization, and Catalytic Properties of Regioisomeric β-Ketoimine Titanium Complexes for Ethylene Polymerization

IF 3.7 2区化学 Q2 CHEMISTRY, APPLIED

Applied Organometallic Chemistry Pub Date : 2025-01-01 DOI:10.1002/aoc.7967

Pingzhou Huang, Wanjun Tang, Mengyuan Xue, Ming Zhou, Wei Tu, Tingcheng Li, Guangyong Xie

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引用次数: 0

Abstract

Non-metallocene catalysts have shown great potential for modulating the polymer microstructure by changing the ligand structure, but the effects of ligand structure and electronic property of metal center on their catalytic performance remain underexplored. Herein, we designed and synthesized two pairs of isomeric tridentate β-ketoimine complexes TiL_a/TiL_b and TiL_c/TiL_d with methylthioaniline and methylthioethylamine side arms, respectively, which exhibited moderate to extremely high activity over 10⁶ g (mol Ti)⁻¹· h⁻¹·atm⁻¹ for the polymerization of ethylene and the copolymerization of ethylene with α-olefins (1-hexene, 1-octene) and polar comonomer (9-decen-1-ol) in the presence of MAO, with the catalytic activities in the order: TiL_d > TiL_c > TiL_a > TiL_b. The regioisomers TiL_c and TiL_d with methylthioethylamine side arm showed significantly higher activity for ethylene (co)polymerization than that of the isomeric TiL_a and TiL_b with methylthioaniline side arm, especially for ethylene copolymerization with α-olefins or polar comonomer 9-decen-1-ol, indicating an obvious positive “comonomer effect”. The complex TiL_d exhibited the highest ethylene (co)polymerization activity and comonomer insertion rate. Structural optimization using density functional theory (DFT) calculations suggested that the “side arms” and the electronic properties of titanium in β-ketoimine titanium complexes played a key role for ethylene polymerization and copolymerization.

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来源期刊

Applied Organometallic Chemistry 化学-无机化学与核化学

CiteScore

7.80

自引率

10.30%

发文量

408

审稿时长

2.2 months

期刊介绍： All new compounds should be satisfactorily identified and proof of their structure given according to generally accepted standards. Structural reports, such as papers exclusively dealing with synthesis and characterization, analytical techniques, or X-ray diffraction studies of metal-organic or organometallic compounds will not be considered. The editors reserve the right to refuse without peer review any manuscript that does not comply with the aims and scope of the journal. Applied Organometallic Chemistry publishes Full Papers, Reviews, Mini Reviews and Communications of scientific research in all areas of organometallic and metal-organic chemistry involving main group metals, transition metals, lanthanides and actinides. All contributions should contain an explicit application of novel compounds, for instance in materials science, nano science, catalysis, chemical vapour deposition, metal-mediated organic synthesis, polymers, bio-organometallics, metallo-therapy, metallo-diagnostics and medicine. Reviews of books covering aspects of the fields of focus are also published.