Zhang Qiurui, Zhang Wenjuan, Rajendran Natesan Mannangatti, Liang Tongling, Sun Wen-Hua
School of Materials Science and Engineering, Beijing Institute of Fashion Technology, Beijing 100029, China.
Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Dalton Trans. 2017 Jun 28;46(24):7833-7843. doi: 10.1039/c7dt01720k. Epub 2017 Jun 8.
A series of highly sensitive aluminum hydroquinolin-8-olates (C1-C8) was synthesized and characterized by H/C NMR spectroscopy. The molecular structures of compounds C1, C3, C4, and C5 were confirmed by single crystal X-ray crystallography and demonstrated the binuclear form. In the presence of BnOH, all the aluminum complexes exhibited moderate to high activities towards the ring-opening polymerization of ε-CL at high temperatures, but quite low activities at ambient temperature. Microstructure analysis of the resultant polycaprolactones showed that the polymers were linear in nature with a BnO- end group. In addition, the mechanism was investigated by monitoring the H NMR and Al NMR of C1 and these results suggested that the complexes existed as dimeric species at low temperature and partly converted into active mononuclear species at higher temperatures, which was easily coordinated by BnOH to afford the active species for the ring-opening polymerization of ε-caprolactone.
合成了一系列高灵敏度的8-羟基喹啉铝化合物（C1 - C8），并通过氢/碳核磁共振光谱对其进行了表征。化合物C1、C3、C4和C5的分子结构通过单晶X射线晶体学得到证实，并显示为双核形式。在苄醇存在下，所有铝配合物在高温下对ε-己内酯的开环聚合表现出中等到高的活性，但在室温下活性相当低。对所得聚己内酯的微观结构分析表明，聚合物本质上是线性的，端基为苄氧基。此外，通过监测C1的氢核磁共振和铝核磁共振对反应机理进行了研究，结果表明配合物在低温下以二聚体形式存在，在较高温度下部分转化为活性单核物种，该单核物种很容易与苄醇配位，从而为ε-己内酯的开环聚合提供活性物种。
