Olefin esterification on Amberlyst®15 catalyst: does the esterification site defy thermodynamics?

Kinetics for the reaction between 1-tetradecene and heptanoic acid to make tetradecyl heptanoates on dry Amberlyst(R)15 catalyst at 90 degrees C are extremely complex. Observed kinetics of simultaneous double bond isomerization and esterification cannot be reconciled with a single type of catalytic site. Esterification andmostof the double bond isomerization must occur on separate sites. Relative rates of esterification for tetradecene isomers suggest that adsorption coefficients on the esterification sites follow 1-tetradecene > 2-tetradecene > 3+-tetradecenes. These relative adsorption coefficients imply that, on this esterification site, 2-tetradecene isomerizes to 3-tetradecene faster than 3-tetradecene isomerizes to 2-tetradecene or 4-tetradecene, a truly novel finding not previously reported for any other acidic site. The site where most of the double bond isomerization occurs does not display this behavior, and isomerization of linear tetradecenes proceeds to thermodynamic equilibrium. Kinetic data indicate that esters form when carboxylic acid traps rapidly isomerizing carbenium ions on the catalyst's surface. Competition is fierce for esterification sites among olefins, carboxylic acid, and esters, and olefins occupy few esterification sites. Contrastingly, olefins triumph in competition for isomerization sites, and olefin isomerization is much faster than esterification. Heptanoic acid exists primarily in dimer form, but the monomer form reacts to make esters. A complex kinetic model fit experimental data for double bond isomerization, conversion of olefin to esters, and the distribution of secondary esters that formed over 22 h. [GRAPHICS] .