Scholarlink

<p>Density functional theory (DFT) calculations were employed to elucidate the mechanism of ethylene copolymerization with α-olefins (1-octene) and a polar monomer (9-decen-1-ol) catalyzed by titanium complexes bearing [N, P] ligands. The study systematically evaluates how fluorination versus methylation of the ligand framework influences the catalytic cycle through electronic and steric effects. Results demonstrate that electron-withdrawing fluorine substituents reduce insertion barriers for ethylene homopolymerization and improve incorporation kinetics for 1-octene. Most significantly, fluorination substantially elevates the energy barrier for <i>β</i>‑hydride elimination in systems containing 9‑decen‑1‑ol, thereby suppressing chain termination and facilitating the production of higher molecular weight polar-functionalized copolymers. Non‑covalent interaction analyses further reveal enhanced catalyst-monomer associations, correlating with higher activity. This work establishes a predictive DFT model that directly links ligand architecture to polymerization performance, offering a rational design strategy for next‑generation catalysts toward functionalized polyolefins.</p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

A DFT-based mechanistic and catalyst design study on the copolymerization of ethylene with polar monomers catalyzed by [N, P]Ti complexes

  • 期刊论文

  • 发表日期：

    2026年4月17日

查看全文
  • Jiaojiao Zhang,
  • Wenqi Wu,
  • Wenwen Cong,
  • Xia Chen,
  • Qihang Sun,
  • Jielun Cao,
  • Yi Li

摘要

Density functional theory (DFT) calculations were employed to elucidate the mechanism of ethylene copolymerization with α-olefins (1-octene) and a polar monomer (9-decen-1-ol) catalyzed by titanium complexes bearing [N, P] ligands. The study systematically evaluates how fluorination versus methylation of the ligand framework influences the catalytic cycle through electronic and steric effects. Results demonstrate that electron-withdrawing fluorine substituents reduce insertion barriers for ethylene homopolymerization and improve incorporation kinetics for 1-octene. Most significantly, fluorination substantially elevates the energy barrier for β‑hydride elimination in systems containing 9‑decen‑1‑ol, thereby suppressing chain termination and facilitating the production of higher molecular weight polar-functionalized copolymers. Non‑covalent interaction analyses further reveal enhanced catalyst-monomer associations, correlating with higher activity. This work establishes a predictive DFT model that directly links ligand architecture to polymerization performance, offering a rational design strategy for next‑generation catalysts toward functionalized polyolefins.