在单位烯聚合过程中显著的反效应. 离子对结构和动态与聚合活性,链转移和联合选择性的相关性
Ming-Chou Chen1, John A S Roberts, Tobin J Marks
1Department of Chemistry, Northwestern University, Evanston, Illinois 60208-3113, USA.
Journal of the American Chemical Society
|April 9, 2004
概括
反阴离子显著影响基预催化剂的烯聚合,影响活性,立体化学和链转移. 较强的离子与对离子的配对导致较高的协同作用力和分子量,温度依赖性较小.
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:
- 齐尔科诺预催化剂对于烯聚合是至关重要的.
- 反离子的选择极大地影响了催化剂性能和聚合物特性.
- 了解离子配对是控制聚合结果的关键.
研究的目的:
- 为了研究对抗离子对综合性烯聚合的速率和立体化学的影响.
- 阐明离子配对特征和聚合行为之间的关系.
- 确定不同对抗离子如何影响催化剂活性,聚合物微观结构和链转移.
主要方法:
- 合成和表征与各种对抗离子的齐尔科诺前催化剂复合物.
- 在不同温度和压力下进行烯聚合实验.
- 聚合物微结构 (综合性,立体缺陷) 和分子重量的分析.
- 使用EXSY和动态NMR对离子对重组的研究.
主要成果:
- 具有较弱离子配对的对抗离子 (例如,B(C6F5) 3-,B(2-C6F5C6F4) 3-) 显示出更高的催化剂活性.
- 强烈协调的对抗离子 (例如,FAl(2-C6F5C6F4) 3-) 产生更高的协同毒性和分子量,温度依赖性降低.
- 离子配对强度调节立体缺陷生成和链传输过程.
结论:
- 反离子结构和离子配对显著控制烯聚合动力学和立体选择性.
- 观察到的效应归因于对立体缺陷产生途径和终结率的调制.
- 溶剂选择可以减少对抗离子效应,这表明聚合控制中的因素的复杂相互作用.
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