基于-α-胺基的乙烯聚合的高性能催化剂的理论设计
Pavee Apilardmongkol1, Manussada Ratanasak2, Tatiya Chokbunpiam3
1Center of Excellence in Computational Chemistry, Department of Chemistry, Faculty of Science, Chulalongkorn University, Pathumwan, Bangkok 10330, Thailand. Vudhichai.P@chula.ac.th.
这项研究使用DFT计算来了解乙烯聚合的Ni-α-diimine催化剂. (II),Rh (II),Pd (II),Fe (II) 和Ru (II) 在开发高活性催化剂方面表现有前途.
科学领域:
- 催化剂是一种催化剂.
- 有机金属化学 有机金属化学
- 聚合物科学 聚合物科学
背景情况:
- α-二胺复合物是烯聚合的关键催化剂.
- 了解反应机制是设计高效催化剂的关键.
研究的目的:
- 研究Ni-α-diimine催化剂用于乙烯聚合的反应机制.
- 确定控制催化剂性能的结构和电子因素.
- 为下一代催化剂确定有前途的过渡金属.
主要方法:
- 使用密度函数理论 (DFT) 的计算.
- 分析了催化剂前的稳定性和反应途径.
- 计算的协调自由能量 (Gc1) 和激活自由能量 (ΔG‡1).
主要成果:
- 第一个乙烯插入是决定速度的步骤.
- 根据性能,M-α-二胺催化剂被分为三组.
- 一个有前途的集群包括具有中等结合和激活能量的Ni (II),Ru (II),Mn (II),Rh (II) 和Pd (II).
- 确定了Mn (II),Rh (II),Pd (II),Fe (II) 和Ru (II) 是强有力的候选物.
- 债券距离和百分比埋藏体积 (%VBur) 是关键的固态因素.
结论:
- DFT计算为设计M-α-二胺催化剂提供了一个合理的框架.
- 优化的固体和电子特性可以增强乙烯聚合过程中的催化剂活性.
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