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Boryloxy Titanium Complex-Enabled High Polar Monomer Contents in Catalytic Copolymerization of Olefins.

Authors :
Wei C
Guo L
Zhu C
Cui C
Source :
Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2025 Jan 10; Vol. 64 (2), pp. e202414464. Date of Electronic Publication: 2024 Oct 22.
Publication Year :
2025

Abstract

The preparation of polyolefins with high polar monomer contents (above 20 mol %) has long been a challenge. Half-titanocenes (Cp')[HCN(Ar)] <subscript>2</subscript> BOTiCl <subscript>2</subscript> bearing bulky electron-donating N-heterocyclic boryloxy ligands have been designed and synthesized. The complexes (Cp*)[HCN(Ar)] <subscript>2</subscript> BOTiCl <subscript>2</subscript> (2, Ar=2,6-iPr <subscript>2</subscript> C <subscript>6</subscript> H <subscript>3</subscript> ; 5, Ar=2,4,6-Me <subscript>3</subscript> C <subscript>6</subscript> H <subscript>2</subscript> ) supported by Cp* and the boryloxy ligands have been shown to efficiently catalyze the copolymerization of ethylene and long chain α-olefins. In particular, precatalyst 5 enabled the controlled synthesis of poly(ethylene-co-9-decen-1-ol) with unprecedented high polar monomer contents up to 32.1 mol % while maintaining the high catalytic activity. The structural analysis and DFT calculations disclosed that the bulky and strong electron-donating boryloxy ligands could effectively stabilize cationic active species. The mechanical studies on the hydroxyl-functionalized copolymers disclosed that they exhibited high strength and toughness because of the existence of hydrogen bonds in the polymer network.<br /> (© 2024 Wiley-VCH GmbH.)

Details

Language :
English
ISSN :
1521-3773
Volume :
64
Issue :
2
Database :
MEDLINE
Journal :
Angewandte Chemie (International ed. in English)
Publication Type :
Academic Journal
Accession number :
39189662
Full Text :
https://doi.org/10.1002/anie.202414464