Mechanistic Studies of Hafnium-Pyridyl Amido-Catalyzed 1‑Octene Polymerization and Chain Transfer Using Quench-Labeling Methods

Chromophore quench-labeling applied to 1-octene polymerization as catalyzed by hafnium-pyridyl amido precursors enables quantification of the amount of active catalyst and observation of the molecular weight distribution (MWD) of Hf-bound polymers via UV-GPC analysis. Comparison of the UV-detected MWD with the MWD of the “bulk” (all polymers, from RI-GPC analysis) provides important mechanistic information. The time evolution of the dual-detection GPC data, concentration of active catalyst, and monomer consumption suggests optimal activation conditions for the Hf pre-catalyst in the presence of the activator [Ph₃C]­[B­(C₆F₅)₄]. The chromophore quench-labeling agents do not react with the chain-transfer agent ZnEt₂ under the reaction conditions. Thus, Hf-bound polymeryls are selectively labeled in the presence of zinc-polymeryls. Quench-labeling studies in the presence of ZnEt₂ reveal that ZnEt₂ does not influence the rate of propagation at the Hf center, and chain transfer of Hf-bound polymers to ZnEt₂ is fast and quasi-irreversible. The quench-label techniques represent a means to study commercial polymerization catalysts that operate with high efficiency at low catalyst concentrations without the need for specialized equipment