Azo-Containing Polymers with Degradation On-Demand Feature

Abstract

Molecules comprising aliphatic azo moieties are widely used as radical polymerization initiators, but only a few studies have explored their usefulness as stimuli-responsive motifs in macromolecular constructs. The controlled degradation of azo-containing polymers has indeed remained largely unexplored. Here we present the syntheses of linear azo-containing polyamides and polyurethanes and report on their thermally and optically induced responses in solution and the solid state. We show that the stimuli-induced degradation behavior depends strongly on the nature of the polymer backbone, the state of matter, and in solution, on the nature of the solvent. The stimuli-responsive solid-state properties of the azo-containing materials may be particularly useful. In the case of the polyurethanes studied here, temperature- or light-induced cleavage of the azo motifs led to a controllable decrease in the molecular weight, which, in turn, caused a reduction of the elongation at break, modulus, and strength. The co...