Abstract：
Anionic polymerizations are of exceptional practical importance, but difficult to analyze due to the high reactivity of the growing polymer chains. Here, we demonstrate that electrospray-ionization mass spectrometry (ESI-MS) permits direct observation of the active carbanionic intermediates formed in the anionic ring-opening polymerization of 1-cyanocyclopropanecarboxylate in tetrahydrofuran. This includes the identification of a side product, as well as real-time analysis of the polymerization reaction. From the mass spectra obtained, we can derive not only the mean molar mass and the polydispersity, but also the rate constants for the initiation and the individual propagation steps. The initiation proceeds significantly faster than the propagation steps. Accordingly, the examined reaction corresponds to a living polymerization, as we also confirmed by additional control experiments. Besides giving detailed insight into the reaction system probed here, we also expect the presented methodology to make possible the in-situ analysis of further anionic polymerizations.
摘要：
阴离子聚合具有特殊的实际重要性，但由于增长的聚合物链的高反应性，难以分析。这里,我们证明了电喷雾电离质谱（ESI-MS）允许直接观察在四氢呋喃中1-氰基环丙烷-羧酸盐的阴离子开环聚合中形成的活性碳阴离子中间体。这包括识别副产品，以及聚合反应的实时分析。从获得的质谱中，我们不仅可以得出平均摩尔质量和多分散性，以及起始和各个传播步骤的速率常数。引发的速度明显快于传播步骤。因此，所检查的反应对应于活性聚合，正如我们还通过其他对照实验证实的那样。除了详细了解这里探测的反应系统，我们希望提出的方法，使进一步的阴离子聚合的原位分析以及。
