Synthesis of dialkyl hexamethylenedicarbamate from 1,6-hexamethylenediamine and alkyl carbamate over Y(NO3)3·6H2O catalyst

The non-phosgene carbonylation of 1,6-hexamethylenediamine (HDA) with alkyl carbamates using Y(NO3)3·6H2O as a catalyst and the influence of reaction variables on the yields of dialkyl hexamethylenedicarbamate (HDC) were studied. At 453 K and in the presence of 5 wt.% Y(NO3)3·6H2O, nearly 100% HDA conversion and 85% dibutyl hexamethylenedicarbamate (BHDC) isolated yield could be achieved when butyl carbamate (BC) was employed as a carbonyl source. During reaction, an induction period was observed, but it almost disappeared by pretreating the catalyst with n-butanol. The FT-IR, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) characterizations of the catalyst showed that some transformation occurred when the catalyst was pretreated with n-butanol or employed during reaction, i.e., part decomposition of Y(NO3)3 to Y2O3, conversion from crystal to amorphous state, changes occurring in chemical state of the active species, as well as some subtle interactions between the catalyst and n-butanol. All these observed changes might be the reason resulting in activation of the catalyst.

At 453 K and in n-butanol, non-phosgene synthesis of dibutyl hexamethylenedicarbamate (BHDC) from butyl carbamate could be achieved with nearly 100% conversion of 1,6-hexamethylenediamine and 85% isolated yield of BHDC over Y(NO3)3·6H2O catalyst. During reaction, an induction period for the catalyst was observed, the FT-IR, XRD and XPS analysis verified that some transformations for the catalyst occurred during the reaction.Figure optionsDownload as PowerPoint slide