Carbon-13 NMR studies of the reactions of crosslinked poly(methyl acrylate) beads with multifunctional amines

Abstract

The kinetics of the functionalization of cross-linked poly(methyl acrylate) beads swollen in dimethylformamide by reactions with various amines was studied by CP/MAS solid-state 13 C NMR using the dipolar dephasing technique. In the presence of excess n-hexylamine the reaction is first order and the kinetics are unaffected by the diffusion process. However, deviation from simple first-order behavior is observed at high conversions for the reactions with the multifunctional amines 1,6-diaminohexane and tris-(2-aminoethyl)amine due to the formation of additional cross-links that hinder the diffusion of these amines within the polymeric beads