Polymerization of 4-methylpentene and vinylcyclohexane by amine bis(phenolate) titanium and zirconium complexes

• Published in: Journal of polymer science. Part A, Polymer chemistry Vol. 44; no. 3; pp. 1136 - 1146
• Main Authors: Gendler, Shimrit, Groysman, Stanislav, Goldschmidt, Zeev, Shuster, Michael, Kol, Moshe
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc., A Wiley Company 01-02-2006; Wiley
• Subjects: Applied sciences; atactic; Exact sciences and technology; living polymerization; Organic polymers; Physicochemistry of polymers; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; Ziegler-Natta polymerization; Substituent effect; Ziegler-Natta polymerization; Bulk polymerization; 4-Methyl-1-pentene polymer; Titanium complex; Aryloxy complex; Zirconium Organic compounds; Complex catalyst polymerization; Zirconium complex; Complex catalyst; Experimental study; atactic; Titanium Organic compounds; Polyvinyl derivative; living polymerization; Olefin polymer; Organic borane; Hexene polymer; Catalyst activity
• ISSN: 0887-624X; 1099-0518
• DOI: 10.1002/pola.21225

The polymerization of the substituted olefins 4‐methylpentene and vinylcyclohexane by dibenzyl titanium and zirconium complexes of three amine bis(phenolate) ligands is reported. The ligands featured a dimethylamino side‐arm donor and either electron‐withdrawing (Cl and Br) or methyl phenolate substituents. After activation with B(C6F5)3, the zirconium catalysts exhibited a higher activity than the titanium catalysts toward these bulky olefins. Very high weight‐average molecular weight poly(4‐methylpentene) was obtained with the zirconium catalysts. The zirconium catalysts were employed in 1‐hexene polymerization, and their activity was found to be the highest ever reported for catalysts of the amine bis(phenolate) family. The catalysts featuring methyl phenolate substituents showed a higher activity toward these substituted olefins than the electron‐poor catalysts; this trend was opposite to their activity toward 1‐hexene. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1136–1146, 2006
The polymerization of the substituted olefins 4‐methylpentene and vinylcyclohexane by amine bis(phenolate) titanium and zirconium complexes was investigated. Both titanium and zirconium complexes were found to be efficient catalysts for the polymerization of these monomers. The zirconium catalysts were more active than the titanium catalysts and yielded high‐molecular‐weight poly(4‐methylpentene). The new zirconium catalysts were also investigated for the polymerization of 1‐hexene. Their activity was found to be monomer‐dependent: the most active catalysts toward 1‐hexene included electron‐withdrawing (Cl and Br) substituents on the ligand's phenolate rings, whereas the most active catalyst toward 4‐methylpentene and vinylcyclohexane included methyl phenolate substituents.