In this work, fundamental insight into the multifaceted role of co-catalyst in activation, propagation, and chain exchange of vanadocene in the immobilized single-site olefin polymerization catalyst has been obtained. The kinetics were followed for various Al/V ratios, at the same polymerization temperature with aluminium diethyl monochloride (DEAC) or triisobutylaluminium (TIBA) as co-catalyst. The results put forward a plausible deactivation reaction path of the catalyst for aluminium diethyl monochloride (DEAC) with irregular morphology of polyethylene particle due to the interaction between halogen atom and vanadium atom. This experimental set of data is supported by a computational investigation at the DFT level that rationalizes specific effects in the presence of co-catalyst at the molecular scale. This joint investigation offers a basic understanding for further catalyst developments in the field of supported metallocene catalyst for olefin polymerization.

在这项工作中，已经获得了在固定化单中心烯烃聚合催化剂中钒催化剂在活化，扩散和链交换中助催化剂的多方面作用的基本见识。在相同的聚合温度下，以二乙基一氯化铝（DEAC）或三异丁基铝（TIBA）作为助催化剂，跟踪各种Al / V比例的动力学。研究结果提出了由于卤素原子和钒原子之间的相互作用，聚乙烯颗粒形态不规则的二乙基二氯化铝（DEAC）催化剂的合理失活路径。此实验数据集得到DFT级别的计算研究的支持，该研究合理化了在分子规模存在助催化剂的情况下的特定作用。