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

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Title:	A DFT-based mechanistic and catalyst design study on the copolymerization of ethylene with polar monomers catalyzed by [N, P]Ti complexes.
Authors:	Zhang, Jiaojiao¹ (AUTHOR), Wu, Wenqi² (AUTHOR), Cong, Wenwen¹ (AUTHOR), Chen, Xia¹ (AUTHOR), Sun, Qihang¹ (AUTHOR), Cao, Jielun¹ (AUTHOR), Li, Yi³ (AUTHOR) liyi@licp.cas.cn
Source:	Journal of Polymer Research. May2026, Vol. 33 Issue 5, p1-13. 13p.
Subjects:	Copolymerization, Titanium catalysts, Monomers, Density functional theory, Ligands (Chemistry), Fluorine, Polyolefins, Ethylene
Abstract:	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. [ABSTRACT FROM AUTHOR]
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Database:	Engineering Source

Description
Abstract:	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. [ABSTRACT FROM AUTHOR]
ISSN:	10229760
DOI:	10.1007/s10965-026-04901-x