Polymeric oxidizing reagents based on polyacrylamides: effect of the nature and extent of crosslinking on reactivity

Abstract

Acrylamide was copolymerized with N,N'-methylene-bis-acrylamide (NNMBA), tetraethyl-eneglycol diacrylate (TEGDA), and divinyl benzene (DVB) in different proportions to afford crosslinked polyacrylamides with varying nature and extent of crosslinking. These insoluble polymers were functionalized with the N-bromoamide function and the reactivity of the resulting polymeric N-bromoamide was investigated under different conditions. The capacities of the reagents varied from 6.7 mequiv / g for the linear polymeric reagent to 1.1 mequiv / g for the 15% DVB-crosslinked reagent. Oxidation of benzoin to benzil was used as the model reaction. Investigation of the reaction under different conditions of solvent and varying molar excess revealed a significant influence of the nature and extent of crosslinking in deciding the extent of reaction. In the case of NNMBA-crosslinked reagents, the reactivity increased up to 10% crosslinking and then decreased. The reactivity of the reagents increased up to 15% crosslinking in the case of TEGDA-crosslinked ones and for DVB-crosslinked reagents the reactivity decreased with crosslinking. The polarity of the crosslinking agent and its molar percentage on the polymeric reagent (crosslink density) are factors affecting the solvent compatibility, which in turn, is decisive in the facilitation of the reactions.