title: Polyamide synthesis from 6-aminocapronitrile, part 1: N-alkyl amide formation by amine amidation of a hydrolyzed nitrile.
abstract: The synthesis of N-hexylpentanamide from a stoichiometric amount of pentanenitrile and hexylamine has been studied as a model reaction for the synthesis of nylon-6 from 6-aminocapronitrile. The reaction was carried out under mild hydrothermal conditions and in the presence of a homogeneous ruthenium catalyst. For the mild hydrothermal conditions the presence of hexylamine distinctively increases the nitrile hydrolysis compared to the nitrile hydrolysis in the absence of hexylamine. Amine-catalyzed nitrile hydrolysis mainly produces the N-substituted amide. A clear product development is observed, consisting of first the terminal amide formation and second the accumulation of N-hexylpentanamide. With a maximum conversion of only 80 % after 18 h, the nitrile hydrolysis rate at 230 degrees C is still much too low for nylon-6 synthesis. Ruthenium dihydride phosphine was therefore used as a homogeneous catalyst, which significantly increases the nitrile hydrolysis rate. At a temperature of 140 degrees C and with only 0.5 mol % [RuH(2)(PPh(3))(4)] a 60 % nitrile conversion is already reached within 2 h. Initially the terminal amide is the sole product, which is gradually converted into N-hexylpentanamide. The reaction has a high initial rate, however, for higher conversions a strong decrease in hydrolysis rate is observed. This is ascribed to product inhibition, which results from the equilibrium nature of the reaction.
authors.affiliation: Laboratory of Polymer Chemistry, Eindhoven University of Technology, 5600 MB Eindhoven, The Netherlands.
authors.forename: Adrianus J M
authors.initials: AJ
authors.lastname: van Dijk
authors.forename: Tom
authors.initials: T
authors.lastname: Heyligen
authors.forename: Robbert
authors.initials: R
authors.lastname: Duchateau
authors.forename: Jan
authors.initials: J
authors.lastname: Meuldijk
authors.forename: Cor E
authors.initials: CE
authors.lastname: Koning