Highlight on the Mechanism of Linear Polyamidoamine Degradation in Water

Abstract

This paper aims at elucidating the degradation mechanism of linear polyamidoamines (PAAs) in water. PAAs are synthesized by the aza-Michael polyaddition of prim-monoamines or bis-sec-amines with bisacrylamides. Many PAAs are water-soluble and have potential for biotechnological applications and as flame-retardants. PAAs have long been known to degrade in water at pH ≥ 7, but their degradation mechanism has never been explored in detail. Filling this gap was necessary to assess the suitability of PAAs for the above applications. To this aim, a small library of nine PAAs was expressly synthesized and their degradation mechanism in aqueous solution studied by 1H-NMR in different conditions of pH and temperature. The main degradation mechanism was in all cases the retro-aza-Michael reaction triggered by dilution but, in some cases, hints were detected of concurrent hydrolytic degradation. Most PAAs were stable at pH 4.0; all degraded at pH 7.0 and 9.0. Initially, the degradation rate was faster at pH 9.0 than at pH 7.0, but the percent degradation after 97 days was mostly lower. In most cases, at pH 7.0 the degradation followed first order kinetics. The degradation rates mainly depended on the basicity of the amine monomers. More basic amines acted as better leaving groups.