Ultrasonic degradation of macromolecules in solution. Study of degradation kinetics by estimation of free-radical scavenger DPPH and solution viscosity measurements

Abstract

The kinetics of degradation of butyl rubber in two solvents, cyclohexane and toluene, was studied by two independent techniques: viscosity measurements and free-radical estimation as a function of DPPH consumed. The general shape of the rate curves in the two cases is similar, but not identical. The rate given by estimation of DPPH is faster than that obtained from solution viscosity data. This has been attributed to the inherent limitations of the two methods for the quantitative determination of the number of breaks occurring in the polymer molecules. The rate is also reduced as the viscosity of the solution medium is increased, which may be correlated with the reduction of the cavitation effect responsible for degradation. The degradation rates in two solvent media initially having the same viscosity were unequal. This may be due to different solvent-solute characteristics, which means that the viscosity and cavitation change to different extents in the two cases throughout the course of degradation. The limiting degree of Polymerization (DP)_∝ obtained after prolonged irradiation has been found to be dependent on parameters such as intensity of irradiation, solution viscosity, and initial DP of the molecules.