Phosgene-free decomposition of dimethylhexane-1,6-dicarbamate over ZnO |
| |
Authors: | Min Jeong Hyun Mi Shin Yong Jin Kim Young-Woong Suh |
| |
Institution: | 1.Department of Chemical Engineering,Hanyang University,Seoul,Republic of Korea;2.Green Process Material Research Group,Korea Institute of Industrial Technology,Cheonan,Republic of Korea |
| |
Abstract: | In catalytic decomposition of dimethylhexane-1,6-dicarbamate (HDC) into hexamethylene-1,6-diisocyanate (HDI), Zn-containing homogeneous (i.e., zinc acetate) and heterogeneous (i.e., ZnO) catalysts were active among a number of catalysts tested, due to the great electron withdrawing ability of Zn ions. Particularly, when polyethylene glycol dimethyl ether was used as a solvent, ZnO was found to be relatively robust, because the catalytic performance was maintained up to the third use (HDC conversion of 93 % and HDI yield of 67 % at 180 °C for 1 h). Through investigation of a HDC/ZnO mixture at elevated temperatures by IR spectroscopy, a possible reaction scheme of ZnO-catalyzed decomposition of HDC was proposed. The H atom is removed from the N–H group of HDC by hydrogen bonding with an O site on the ZnO surface, followed by coordination of an O–C=O group in monodentate mode to a Zn site. The C–O group in the O–C=O linkage is then cleaved yielding the isocyanate and surface methoxide species. Finally, methanol is released from ZnO by a reaction between the surface methoxide and the hydroxyl species. |
| |
Keywords: | |
本文献已被 SpringerLink 等数据库收录! |
|