乙烯的活聚合由含的基复合物催化,具有含的氧胺酸联体
Makoto Mitani1, Jun-ichi Mohri, Yasunori Yoshida
1R & D Center, Mitsui Chemicals, Inc., 580-32 Nagaura, Sodegaura, Chiba 299-0265, Japan.
Journal of the American Chemical Society
|March 28, 2002
概括
新的复合物与含联体使活乙烯聚合成为可能,产生高分子量聚合物. 离子相邻的的存在是高温控制和独特的块共聚合物合成的关键.
科学领域:
- 有机金属化学 有机金属化学
- 聚合物科学 聚合物科学
- 催化剂是一种催化剂.
背景情况:
- 复合物与氧胺联体被探索为olefin聚合.
- 替代在配体上可以影响催化剂活性和选择性.
- 活聚合对于受控的聚合物架构和块共聚合物合成至关重要.
研究的目的:
- 合成和描述具有不同替代模式的新型复合物.
- 在乙烯聚合过程中研究这些复合物的催化性能.
- 确定原子位置对聚合行为和聚合物性质的作用.
主要方法:
- 通过化氧胺联体的盐与TiCl的反应合成七个复合物.
- 使用X射线衍射分析进行结构性表征.
- 用乙烯和甲基氧 (MAO) 作为不同温度的共催化剂对催化活性和聚合控制的评估.
主要成果:
- 综合体1和3呈现出扭曲的八面体结构与跨氧氧.
- 复合物1/MAO系统证明了活乙烯聚合,产生高分子量聚乙烯 (M(n) >400,000) 具有狭窄的多分散性 (M(w) /M(n) <1.20).
- 催化剂与相邻的imine (复合物2-4) 在50°C实现了活聚合,而其他催化剂 (复合物5-7) 显示β-转移.
结论:
- 原子与酸相邻,对于高温活乙烯聚合是必不可少的.
- 原子可能与聚合物的β-相互作用,防止链条终结.
- 开发的催化剂系统可以合成独特的聚乙烯基块共聚合物.
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