Synthesis and kinetics of 2,5-dicyanofuran in the presence of hydroxylamine ionic liquid salts

摘要

2,5-Dicyanofuran(DCF)is an important biomass-derived platform compound primarily used to prepare bio-based adiponitrile,which is the key precursor for the synthesis of nylon 66 and 1,6-hexanediisocyanate(HDI).In this study,one-pot,green and safe synthesis of DCF from 2,5-diformylfuran(DFF)and hydroxylamine ionic liquid salts was proposed.Eco-friendly hydroxylamine ionic liquid salts were used as the nitrogen source.Ionic liquid exhibited three-fold function of cosolvent,catalysis and phase separation.The conversion of DFF and yield of DCF reached 100%under the following optimum reaction conditions:temperature of 120
C for 70 min,volume ratio of paraxylene:[HSO_(3)-b-Py]
HSO4 of 2:1,and molar ratio of DFF:(NH_(2)OH)_(2)
[HSO_(3)-b-Py]
HSO4 of 1:1.5.The reaction mechanism for the synthesis of DCF was proposed,and the kinetic model was established.The reaction order with respect to DFF and intermediate product 2,5-diformylfuran dioxime(DFFD)was 1.06 and 0.16,and the reaction activation energy was 64.07 kJ
mol1 and 59.37 kJ
mol1 respectively.After the reaction,the ionic liquid was easy to separate,recover and recycle.