双甲基和双甲基酸盐在乙烯中显示的聚合物高于二聚体:通过PFG NMR进行分子扩散研究和聚合-活性相关性
Xiulan Xie1, Carsten Auel, Wolfram Henze
1Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse, D-35032 Marburg, Germany.
使用脉冲场梯度NMR扩散来研究更高的有机酸盐聚合物,如二甲基酸盐. 聚合量大小影响反应性,较大的聚合物减少了与子的添加反应中的反应性.
科学领域:
- 有机金属化学 有机金属化学
- 超分子化学 超分子化学
背景情况:
- 有机酸盐是有机合成中的关键试剂.
- 了解它们的聚合状态对于预测反应性至关重要.
研究的目的:
- 为了确定二甲基酸盐和bis[(trimethylsilyl) methyl]酸盐的较高聚合物的分子大小.
- 为了将总体大小与加法反应中的反应性相关联.
主要方法:
- 脉冲场梯度 (PFG) 在乙烯中进行NMR扩散测量.
- 使用无球体模型和基于结构的模型进行分析.
- 溶解分析以确定溶剂分子的附着.
主要成果:
- 所有研究的酸盐系统都形成了比二次体更大的聚合物.
- 提出了具有同质核的聚合物链模型.
- 总体的长度指数在1.3到5.2之间被确定.
结论:
- 有机酸盐的较高聚合状态降低了它们在加反应中的反应性.
- 聚合的差异解释了和二甲基酸盐之间的反应性差异.
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