Ultrasonic degradation of poly(acrylic acid)

The ultrasonic degradation of poly(acrylic acid), a water‐soluble polymer, was studied in the presence of persulfates at different temperatures in binary solvent mixtures of methanol and water. The degraded samples were analyzed by gel permeation chromatography for the time evolution of the molecular weight distributions. A continuous distribution kinetics model based on midpoint chain scission was developed, and the degradation rate coefficients were determined. The decline in the rate of degradation of poly(acrylic acid) with increasing temperature and with an increment in the methanol content in the binary solvent mixture of methanol and water was attributed to the increased vapor pressure of the solutions. The experimental data showed an augmentation of the degradation rate of the polymer with increasing oxidizing agent (persulfate) concentrations. Different concentrations of three persulfates—potassium persulfate, ammonium persulfate, and sodium persulfate—were used. It was found that the ratio of the polymer degradation rate coefficient to the dissociation rate constant of the persulfate was constant. This implies that the ultrasonic degradation rate of poly(acrylic acid) can be determined a priori in the presence of any initiator. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009