Catalysis Letters, Vol.99, No.3-4, 133-140, 2005
Amination of alcohols, using Cu/Ni-based colloidal catalyst, for consecutive reaction system
Animation of dodecyl alcohol and monomethylamine (MMA, di-functional) using Cu/Ni-based colloidal catalyst stabilized by barium stearate, and its kinetic study were performed to effectively synthesize didodecylmethylamine (DDMA). For the initial 3-4 h when MMA/dodecyl alcohol mole ratio was less than 1, the amination reaction proceeded very fast (72 mole-alcohol h(-1) mole-Cu at 200degrees) by zero-order kinetics to directly produce DDMA (85%), with complete consumption of MMA, without liberation of the intermediate, momomethyldodecylamine (MMDA) at all. Then, immediately after the mole ratio exceeded 1, the amination proceeded very slowly (3.4 mole-alcohol h(-1) mole-Cu) by consecutive mechanism (second order) with liberation of MMDA. Aldolization of dodecyl aldehyde, formed by dehydrogenation of dodecyl alcohol, was found to be catalyzed by methylamines. Maintaining the zero-order kinetics by continuous control of MMA/alcohol mole ratio at less than 1 through out the amination is essential to obtain a highest DDMA yield by preventing the unwanted aldolization and transalkylation of MMA leading to various byproducts. Catalytic activity of the colloidal catalyst was sevenfold active than that of corresponding solid ones. Amination of 1,6-hexanediol and dimethylamine, using the colloidal catalyst and liquid paraffin as a solvent, was proceeded by consecutive mechanism to form N,N,N',N'-tetramethyl-l,6-hexamethylenediamine with an yield of 80%.