串联环开/环闭转化聚合:单体结构和反应性之间的关系
Hyeon Park1, Ho-Keun Lee, Tae-Lim Choi
1Department of Chemistry, Seoul National University, Seoul 151-747, Korea.
Journal of the American Chemical Society
|July 13, 2013
概括
单体设计显著影响了油甲基解聚合的聚合. 这项研究揭示了含有环基和基群的单体中的结构变化如何影响串联环开/环闭转化聚合率和修饰后反应性.
科学领域:
- 聚合物化学 聚合物化学
- 有机合成 有机合成
- 材料科学 材料科学 材料科学
背景情况:
- 环基具有低环应变和1-基因通常是olefin转基因聚合的较差单体.
- 在单个分子内协同的功能组可以提高转化聚合效率.
- 之前的研究表明,通过中继机制,循环烯-甲基单体的快速串联环开/环闭转化 (RO/RCM) 聚合,通过第三代格鲁布斯催化剂实现了活聚合.
研究的目的:
- 为了研究单体结构修改对二联式RO/RCM聚合物的影响.
- 为了阐明合聚合过程的机制.
- 探索调节聚合和后修饰反应的结构-活性关系.
主要方法:
- 用修改的环烯和基因部分合成和表征各种单体.
- 使用格鲁布斯催化剂进行olefin转化聚合.
- 动力学研究以确定聚合率.
- 通过质子核磁共振 ((1) H NMR) 光谱进行终端组分析,以确定聚合机制.
- 迪尔斯-阿尔德反应研究,以评估聚合物修饰后的反应性.
主要成果:
- 单体结构,包括环基环大小,基长度和链接单位,显著影响聚合率.
- 结构修改也影响了多聚化后的迪尔斯-阿尔德反应的反应性.
- 终端组分析证实了合并RO/RCM聚合的基因第一途径.
- 性阻碍单体的成功聚合产生了带有替代环基单元的聚合物.
结论:
- 这项研究确立了双重RO/RCM聚合过程中的显著结构-反应性关系.
- 基因第一机制为理解这些结构-反应性相关性提供了基础.
- 这项研究使得能够设计出新的单体,用于控制合成具有定制性质和功能的聚合物.
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