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Phosgene-free decomposition of dimethylhexane-1,6-dicarbamate over ZnO

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.

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Acknowledgments

This research was supported by the Fusion Research Program for Green Technologies through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT & Future Planning (2012M3C1A1054501).

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Correspondence to Young-Woong Suh.

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Hyun, M.J., Shin, M., Kim, Y.J. et al. Phosgene-free decomposition of dimethylhexane-1,6-dicarbamate over ZnO. Res Chem Intermed 42, 57–70 (2016). https://doi.org/10.1007/s11164-015-2224-x

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  • DOI: https://doi.org/10.1007/s11164-015-2224-x

Keywords

  • Catalytic decomposition
  • Hexamethylene-1,6-diisocyanate
  • Dimethylhexane-1,6-dicarbamate
  • ZnO