| Abstract: | 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 |
