在氧胺Zr-催化乙烯/1-烯共聚化中意外的前催化剂σ-连接物效应
Yanshan Gao1, Matthew D Christianson2, Yang Wang1
1Department of Chemistry , Northwestern University , Evanston , Illinois 60208-3113 , United States.
Journal of the American Chemical Society
|April 25, 2019
概括
金属NR2前体在烯聚合中表现出高活性,使得选择性1 - 八合并成为可能. 这种意想不到的选择性来自于以前被认为是失活的新型催化途径.
科学领域:
- 有机金属化学
- 聚合物科学
背景情况:
- 均的烯酸聚合催化剂通常使用金属Cl或金属基基前体.
- 在olefin聚合研究中,金属NR2的前体尚未得到充分研究.
研究的目的:
- 在乙烯聚合中研究Zr-amido复合物的催化活性和选择性.
- 探索金属NR2前体的潜力,以增强共单体的结合.
主要方法:
- 合成和激活Zr-amido复合体FI2ZrX2 (X = NMe2).
- 用不同度的1-octene进行乙烯聚合实验.
- 使用NMR光谱和X射线衍射进行表征.
- 催化控制实验以阐明激活机制.
主要成果:
- Zr-amido复合体表现出高的乙烯聚合活性.
- 具有显著的1氧乙烯连锁选择性 (高达7.2mol%),优于传统的碳化合物催化剂.
- 确定了一种新型的催化途径,在激活过程中涉及FI联体的抽象.
结论:
- Zr-amido前体可以在具有增强的共单体选择性的情况下对油脂聚合物具有高度有效性.
- 通过三甲意外抽取FI连接物是活性物种形成的关键.
- 研究各种预催化剂配体对于推进4组烯聚合催化剂至关重要.
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