乳化物的双金属聚合与由binaphthol衍生的 bis-heteroscorpionate dizinc 和 dimagnesium 复合物的双金属聚合
Maxym Tansky1, Robert J Comito1
1Department of Chemistry, University of Houston, Houston, Texas 77204-5003, USA. rjcomito@central.uh.edu.
Dalton transactions (Cambridge, England : 2003)
|June 15, 2023
概括
新的模块化双金属催化剂在乳化物聚合过程中表现出增强的反应性,这是由于金属与金属的合作性. 这些催化剂与单金属版本相比,提供了更好的速率,使控制区块共聚合成为可能.
科学领域:
- 聚合物化学 聚合物化学
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
背景情况:
- 离散双金属催化剂在乳聚合过程中提供了增强的反应性和选择性.
- 现有的双核连接体的模块性有限,阻碍了催化剂的优化.
- 金属对金属的合作性是设计高效催化剂的关键原则.
研究的目的:
- 开发用于双核催化剂的模块化连接体系统.
- 为了研究乳聚合中的结构-活性关系.
- 探索双金属催化剂中的金属-金属合作性,以提高聚合率.
主要方法:
- 一个模块化的bis(pyrazolyl) 联体系列的合成,由一种性双单元桥接.
- 制备和表征双金属和复合物.
- 在现场复合和聚合研究使用乳酸和e-caprolactone.
主要成果:
- 确定了联体1-Me2的复合物,作为乳化物聚合的高活性催化剂,性能优于单金属类型.
- 动力学分析显示了第一阶的依赖性,支持金属对金属的合作性.
- 尽管观察到转化,但证明了 ε-caprolactone 和 L-lactide 的受控块共聚合.
结论:
- 模块化连接体系统使双金属催化剂的有效结构反应性分析成为可能.
- 金属对金属的合作性显著提高了聚合率.
- 催化剂通过协调插入机制运作,但对于raceme或meso-lactide没有实现立体选择性.
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