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聚苯胺盐催化二氧化碳与环氧化物的环加成反应。

Cycloaddition of CO2 to epoxides catalyzed by polyaniline salts.

作者信息

He Jinling, Wu Tianbin, Zhang Zhaofu, Ding Kunlun, Han Buxing, Xie Ye, Jiang Tao, Liu Zhimin

机构信息

Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China.

出版信息

Chemistry. 2007;13(24):6992-7. doi: 10.1002/chem.200700210.

Abstract

The catalytic activity of polyaniline-HX (X=I, Br, Cl) (PANI-HI, PANI-HBr, PANI-HCl) for the cycloaddition of CO2 to propylene oxide (PO) to produce propylene carbonate (PC) was studied for the first time. It was shown that all the PANI salts were active for the reaction, and PANI-HI was most active and selective. On the basis of the preliminary results, the effect of the reaction conditions on the cycloadditions of CO2 to propylene oxide and epichlorohydrin was further investigated by using PANI-HI as the catalyst. The results indicated that the optimized temperature was around 115 degrees C. The maxima occurred in yield versus pressure curves at about 5 MPa for both substrates. Complete conversion was achieved in 3 h for epichlorohydrin and 6 h for propylene oxide at 115 degrees C and 5 MPa. With propylene oxide as the substrate, the reusability of PANI-HI was evaluated and no loss of catalytic activity was detectable after the catalyst had been reused five times. The catalyst was characterized by thermogravimetric analysis (TGA) and scanning electron microscopy (SEM), which provided further evidence for the high stability of the catalyst. We believe that the catalyst has great potential for industrial applications because it has some unusual advantages, such as its easy preparation, high activity, selectivity, stability, low cost, and simple separation from products.

摘要

首次研究了聚苯胺 - HX(X = I、Br、Cl)(聚苯胺 - HI、聚苯胺 - HBr、聚苯胺 - HCl)催化二氧化碳与环氧丙烷(PO)环加成生成碳酸丙烯酯(PC)的活性。结果表明,所有聚苯胺盐对该反应均具有活性,其中聚苯胺 - HI活性和选择性最高。基于初步结果,以聚苯胺 - HI为催化剂进一步研究了反应条件对二氧化碳与环氧丙烷和环氧氯丙烷环加成反应的影响。结果表明,优化温度约为115℃。两种底物的产率与压力曲线在约5MPa处出现最大值。在115℃和5MPa下,环氧氯丙烷在3小时内实现完全转化,环氧丙烷在6小时内实现完全转化。以环氧丙烷为底物,对聚苯胺 - HI的可重复使用性进行了评估,催化剂重复使用五次后未检测到催化活性损失。通过热重分析(TGA)和扫描电子显微镜(SEM)对催化剂进行了表征,这为催化剂的高稳定性提供了进一步的证据。我们认为该催化剂具有很大的工业应用潜力,因为它具有一些独特的优势,如易于制备、活性高、选择性好、稳定性高、成本低以及与产物分离简单等。

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