Amine‐derivatized poly(diallyldimethylammonium chloride) from N ‐vinylformamide copolymerization

The reactivity ratios for the aqueous free‐radical copolymerization of diallyldimethylammonium chloride and N ‐vinylformamide were found to be 0.13 and 1.92, respectively, from a Fineman–Ross analysis of a series of batch polymerizations. Because batch polymerization could not give a uniform product in a high yield with two monomers of such different reactivities, a semibatch procedure was developed in which the more reactive N ‐vinylformamide was added in 10 steps over the course of the copolymerization. The poly(diallyldimethyl‐ ammonium chloride‐ co ‐ N ‐vinylformamide) copolymers were hydrolyzed to give poly(diallyldimethylammonium chloride‐ co ‐vinylamine). The utility of the vinylamine/diallyldimethylammonium chloride copolymers was demonstrated by the preparation and characterization of three derivatives: (1) a copolymer with coupled dansyl groups for fluorescence detection; (2) a copolymer with coupled dabsyl groups for ultraviolet–visible detection; and (3) an ultra‐high‐molecular‐weight (1.6 × 10 6 Da) poly(diallyldimethylammonium chloride) by chain extension (coupling) with glycerol diglycidyl ether. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1068–1075, 2007