对Ni (II) 催化非交替乙烯-一氧化碳共聚的机制见解
Maria Voccia1, Lukas Odenwald2, Maximilian Baur2
1Department of Chemistry, University of Salerno, Via Giovanni Paolo II, 84084 Fisciano, Salerno, Italy.
Journal of the American Chemical Society
|August 9, 2022
概括
研究人员发现如何使用乙烯和一氧化碳制造聚乙烯. 这种非交替共聚的突破是开发新功能材料的关键.
科学领域:
- 聚合物化学
- 有机金属化学
- 催化剂
背景情况:
- 乙烯和一氧化碳的非交替共聚化产生具有基团的聚乙烯.
- 酸催化剂使这种反应成为可能.
- 了解反应机制对于催化剂设计至关重要.
研究的目的:
- 阐明乙烯和一氧化碳非交替共聚的机制.
- 确定交替和非交替路径的速率决定步骤.
- 了解催化剂结构在控制共聚物微结构中的作用.
主要方法:
- 催化活性物种的密度功能理论 (DFT) 计算.
- 从压力反应器共聚合物进行的实验性聚合物微结构分析.
- 对各种酸催化剂的研究.
主要成果:
- 非交替结合的速率决定的步骤是-烯酸中间体的 cis/trans 异构化.
- 乙烯结合以打开C,O-酸盐是交替基因形成的决定性步骤.
- 一个特定的Ni (II) 催化剂特征,P结合的芳香分子的η2协调,影响了通路的竞争.
结论:
- 这种机制涉及电子和硬质因素之间的微妙平衡.
- 催化剂设计,特别是连接体的结构约束,可以调整选择性向非交替共聚化.
- 这项工作为设计功能性聚烯的催化剂提供了基本的见解.
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