聚合物结合基的分子间和分子内转移反应的相对速率和近似速率常数
Dennis P Curran1, Fanglong Yang, Jae-Ho Cheong
1Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, USA. curran@pitt.edu
Journal of the American Chemical Society
|December 12, 2002
概括
聚合物结合的基因表现出与溶液中的转移率相当的转移率,这表明基于溶液的速率常数是适用的. 亚利基基通过分子内的抽取是快速的,影响反应性预测.
科学领域:
- 聚合物化学 聚合物化学
- 有机反应机制 有机反应机制
- 物理有机化学 有机化学
背景情况:
- 了解聚合物结合基的反应性对于设计先进材料和合成方法至关重要.
- 转移的反应是激进化学的基础,影响反应路径和产品的形成.
研究的目的:
- 量化涉及聚合物结合基的分子间和分子内转移反应的相对速率和速率常数.
- 为了比较聚合物结合的基因与它们在溶液中的对应物的活性.
- 评估溶液相运动数据对固体支基系统的适用性.
主要方法:
- 使用聚合物结合的初级基和基激素对转移反应的动态测量.
- 树脂结合和溶液相系统之间的反应速率的比较.
- 从聚合物骨干和链接器中抽取分子内的分析.
主要成果:
- 与树脂结合的初级基基因与分支酸相比,与溶液相反应相比,反应速度约为两倍慢.
- 固体和溶液相反应之间的反应速率差异在实际应用中被认为是可以忽略不计的.
- 树脂结合的基从聚合物骨干和链接器 (k = 3 x 10^6 s^-1) 经历了快速的分子内提取.
结论:
- 溶液相速常数可以可靠地应用于聚合物结合的基因.
- 对树脂的简化"溶剂"模型可以帮助预测其他聚合物系统中的分子内效应.
- 虽然快速的分子内循环是可行的,但较慢的循环和双分子反应受到来自聚合物支的竞争性转移的阻碍.
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