Radical Polymerization of Protonated Diallylammonium Monomers in Bidistilled Aqueous Solution: Kinetic Study

The kinetics of the radical polymerization of protonated monomers of the diallylammonium series (diallyl- and diallylmethylammonium trifluoroacetates) in bidistilled aqueous solution (quartz bidistiller) is studied in situ using 1Н NMR spectroscopy. The rates of monomer consumption and polymer accumulation in the range of 30–50°С are determined. For diallylammonium trifluoroacetate, the effective activation energy of polymerization and the constant of chain transfer to the monomer (30°С) are estimated. It is found that the initial rates of polymerization are comparable with the rates of polymerization of quaternized analogs and the constant of chain transfer to the monomer and the activation energy of polymerization are close to the analogous characteristics of polymerization in the case of quaternized diallyldimethylammonium chloride. It is shown that for polymerization in bidistilled solution, the constant of chain transfer to the monomer (30°С, 3.8 × 10–3) is more than three times lower than that for polymerization in monodistillate (30°С, 12.2 × 10–3) and the ММ of the polymers is ~2.4 times higher than the ММ of the samples synthesized in monodistillate under the same conditions. It is ascertained that standard electrolyte admixtures in distilled aqueous solution considerably affect radical chemical reactions involving protonated forms.