Effect of hydrogen donors on polymer degradation

The thermal decomposition of hydrocarbon macromolecules, including polymers in solution, is influenced by the presence of hydrogen donors. Depending on the particular polymer, hydrogen donors may increase, decrease, or have no effect on degradation rate. We investigated the concentration effect of the hydrogen- (H-)donor, 6-hydroxy tetralin, on degradation of polystyrene (2 g/l) dissolved in mineral oil at 275°C. The time evolution of the molecular weight distribution (MWD) was determined by gel permeation chromatography of samples from the batch reactor. The data indicated that the H-donor decreases the polystyrene degradation rate. This is in contrast to the H-donor (tetralin) enhancement of degradation for poly(styrene–allyl alcohol) dissolved in a 1-butanol solution at 150°C. Because the reaction mechanism for polymer degradation involves radicals, we have developed continuous-distribution mass balances for polymers and radicals in the elementary reactions by treating molecular weight as a continuous variable. Based on reactions for initiation–termination, propagation–depropagation and H-abstraction, the model describes the various H-donor effects through relative values of rate coefficients.