作为受控ROMP的高效单体的三环和三环:理解结构-传播速率关系,并使容易的聚合后修饰成为可能
Landon J Kilgallon1, Timothy P McFadden2, Matthew S Sigman2
1Department of Chemistry, Massachusetts Institute of Technology Cambridge MA 02139 USA.
Chemical science
|June 7, 2024
概括
使用格鲁布斯第三代前催化剂的环开放元解聚合 (ROMP) 用于三旋烯 (TCN) 和三旋烯 (TCND) 单体进行了探索. 体因素,而不是电子因素,最好预测聚合率,使新的功能化策略成为可能.
科学领域:
- 聚合物化学 聚合物化学
- 有机合成 有机合成
- 催化剂是一种催化剂.
背景情况:
- 环开放元解聚合 (ROMP) 是聚合物合成的一个关键技术.
- 三克隆纳 (TCN) 和三克隆纳 (TCND) 是ROMP的未充分探索的单体类.
- 了解结构聚合关系对于推进聚合物化学至关重要.
研究的目的:
- 为ROMP合成和比较TCN和TCND单体.
- 调查影响ROMP动态的因素.
- 开发新的聚合后修饰策略.
主要方法:
- 合成TCN和TCND的胺基,单和二.
- 实时1HNMR光谱检测用于监测聚合动力学.
- 密度函数理论 (DFT) 计算用于分析电子和固态参数.
主要成果:
- 对于各种TCN和TCND单体,确定了传播速率 (kp).
- 体参数与电子参数相比,与 kp 的相关性更强.
- 一个TCND二聚体及其聚合物在二醇结合物添加反应中表现出高反应性.
结论:
- 单体结构,特别是体质量,显著影响ROMP动力学.
- DFT分析提供了对结构-聚合率关系的见解.
- 使用TCND聚合物开发了一种新的,无保护组的聚合物功能化方法.
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