The isopropylation of biphenyl over H-mordenite - Roles of 3- and 4-isopropylbiphenyls

摘要

The isopropylation of biphenyl (BP) and 3- and 4-isopropylbiphenyls (3- and 4-IPBPs) was examined over H-mordenites (MOR) to elucidate the mechanism of shape-selective formation of 4,4-diisopropylbiphenyl (4,4'-DIPB). The isopropylation of BP occurred predominantly to form 4-isopropylbiphenyl (4-IPBP) from BP and 4,4'-DIPB from 4-IPBP. However, 3-IPBP, a minor isomer from BP, cannot participate effectively in the formation of 3,4'-DIPB due to steric restriction of its isopropyl moiety with MOR channels. Selective formation of 4,4'-DIPB was observed at low to moderate temperatures: 225-275 °C. However, the selectivities for 4,4'-DIPB were decreased at high temperatures, 300-350 °C under propene pressure, 0.8 MPa, by the isomerization of 4,4'-DIPB at external acid sites. The isomerization of 4,4'-DIPB occurred under low propene pressure even at 250 °C. The roles of 3- and 4-IPBPs in the formation of DIPB isomers were examined in the isopropylation of their mixtures. 4-IPBP was consumed much faster than 3-IPBP in all cases examined. 4-IPBP was an exclusive precursor to DIPB isomers, particularly 4,4'-DIPB. 4,4'-DIPB was also found as a predominant isomer in encapsulated products at all conditions examined. These results show that 4-IPBP can preferentially establish active transition state with propene and acid site in MOR channels, resulting in selective formation of 4,4'-DIPB. It is concluded that the isopropylation of BP over MOR occurs through reactant selectivity mechanism and restricted transition state mechanism, but not through product selectivity mechanism.