Polyamide hydrolysis accelerated by small weak organic acids

It is well known that acidity, pH, of a solution accelerates the hydrolysis of soluble amides. Here we describe the unexpected result that weak small organic acids at low concentrations hydrolyze a polyamide at rates approximately twice that of a water HCl solution of the same pH. The effect of three small organic acids in dilute solutions, acetic, propanoic, and butanoic was studied. It is observed that the effect on the hydrolysis rate increases as the organic acid gets weaker. Butanoic, the weakest acid, has the strongest effect on increasing the hydrolysis rate. Measurements on the concentration of these acids in the polyamide reveal that there is a selective desire for these weak organic acids to diffuse into the polyamide. The concentration of these acids in the polyamide is found to be several multiples of the concentration in the water environment. And the acid concentration is highest for butanoic. The hydrolysis rate is shown to be governed by solubility, not pH of the water environment. The longer hydrocarbon tail on the carboxylic group increases its compatibility with the polyamide's monomer structure. Results are reported on the hydrolysis of polyamide-11 polymerized from aminoundecanoic acid, both neat and a commercial plasticized composition, placed in water at 100 °C and 120 °C under anaerobic conditions in high pressure glass tubes.