由Pd/Ag化交叉脱聚合物加速链延伸引起的Carothers方程的异常
Liwen Xing1, Ji-Ren Liu2,3, Xin Hong2,3
1Molecular Engineering & Sciences Institute, University of Washington, Seattle, Washington 98195, United States.
Journal of the American Chemical Society
|January 31, 2022
概括
这项研究揭示了一种新的聚合方法, 挑战了卡罗瑟方程, 产生了具有最小缺陷的高分子量聚合物. 这项研究揭示了在交叉脱联聚合中有效延长链的独特机制.
科学领域:
- 聚合物化学
- 有机合成
- 催化剂
背景情况:
- 卡罗瑟方程是预测聚合物特性的一种标准模型.
- 捐赠-接受 (D-A) 聚合物在材料科学中至关重要.
- 交叉脱合 (CDC) 是一种强大的聚合技术.
研究的目的:
- 在机理上研究Pd/Ag催化CDC聚合物.
- 使用特定的硫和化双单体合成D-A聚合物.
- 了解为什么反应偏离卡罗瑟方程.
主要方法:
- Pd/Ag可催化交叉脱合 (CDC) 聚合.
- 反应步骤的动力分析.
- 密度函数理论 (DFT) 的计算.
主要成果:
- 第二个链延伸交叉合比第一个和同质合快得多.
- 实现了低同质合缺陷和高分子量聚合物.
- 在第一个合中,C-H键的激活是决定速率的,而不是第二个.
结论:
- 这项研究提出了一种与卡罗瑟方程相矛盾的聚合机制.
- 在过渡状态下增强的Pd-thiophene相互作用加速了第二次交叉合.
- 这些发现为C-H键激活提供了洞察力,并可以帮助合成各种分子.
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