Alkylaluminium is one of the components of the Ziegler-Natta catalysts, which plays a significant role in the active materials with different regions and stereoselectivity. The polymerization of isoprene with alkylaluminium in TiCl₄/MgCl₂ type Ziegler-Natta catalysts system is rarely studied by simulation. In this work, density functional theory (DFT) was applied to investigate the mechanism of the polymerization of isoprene with heterogeneous Ziegler-Natta catalyst in the presence and absence of AlEt₂Cl on the surface of MgCl₂ (110). The interaction between AlEt₂Cl and MgCl₂ support was studied by the counterpoise corrected approach. Two active models were adopted to analyze the influence of AlEt₂Cl on the polymerization of isoprene in the coordination process and the insertion process respectively. The calculations indicated that only one double bond of isoprene was coordinated to the active center, the presence of AlEt₂Cl improved the stereoselectivity of the active center, increased the difficulty of cis coordination, and reduced the difficulty of trans coordination. In the insertion process, the cis insertion process was more favorable and the trans product structure was more stable.

烷基铝是齐格勒-纳塔催化剂的组分之一，在具有不同区域和立体选择性的活性材料中起着重要作用。很少通过模拟研究异戊二烯与烷基铝在TiCl ₄ / MgCl ₂型齐格勒-纳塔催化剂体系中的聚合。在这项工作中，应用密度泛函理论（DFT）研究了在MgCl ₂（110）表面存在和不存在AlEt ₂ Cl的情况下异戊二烯与非均相齐格勒-纳塔催化剂的聚合机理。AlEt ₂ Cl与MgCl ₂之间的相互作用通过平衡地权修正方法研究了支持。采用两个活性模型分别分析了AlEt ₂ Cl在配位过程和插入过程中对异戊二烯聚合的影响。计算表明，异戊二烯只有一个双键与活性中心配位，AlEt ₂ Cl的存在提高了活性中心的立体选择性，增加了顺式配位的难度，降低了反式配位的难度。在插入过程中，顺式插入过程更有利，反式产物结构更稳定。