RESUMEN
The introduction of a secondary interaction is an efficient strategy to modulate transition-metal-catalyzed ethylene (co)polymerization. In this contribution, O-donor groups were suspended on amine-imine ligands to synthesize a series of nickel complexes. By adjusting the interaction between the nickel metal center and the O-donor group on the ligands, these nickel complexes exhibited high activities for ethylene polymerization (up to 3.48 × 106 gPE·molNi-1·h-1) with high molecular weight up to 5.59 × 105 g·mol-1 and produced good polyethylene elastomers (strain recovery (SR) = 69-81%). In addition, these nickel complexes can catalyze the copolymerization of ethylene with vinyl acetic acid, 6-chloro-1-hexene, 10-undecylenic, 10-undecenoic acid, and 10-undecylenic alcohol to prepare the functionalized polyolefins.
RESUMEN
A family of pyridine-oxazoline-ligated cobalt complexes L2CoCl23a-h were synthesized and characterized. Determined via single-crystal X-ray diffraction, complexes 3a and 3d, ligated by two ligands, displayed a distorted tetrahedral coordination of a cobalt center. The X-ray structure indicated the pyridine-oxazoline ligands acted as unusual mono-dentate ligands by coordinating only to Noxazoline. Upon activation with AlEt2Cl (diethylaluminum chloride), these cobalt complexes all exhibited high catalytic activity (up to 2.5 × 106 g·molCo-1·h-1), affording cis-1,4-co-3,4-polyisoprene with molecular weights of 4.4-176 kg mol-1 and a narrow Ð of 1.79-3.42, suggesting a single-site nature of the active sites. The structure of cobalt catalysts and reaction parameters, especially co-catalysts and the reaction temperature, all have significant influence on the polymerization activity but not on the microstructure of polyisoprene.