Determination of multiple thermal degradation mechanisms of poly(3-hydroxybutyrate)

The thermal degradation of poly(3-hydroxybutyrate) (PHB) was investigated by kinetic analyses in detail to clarify its complex degradation behavior, resulting in a finding of mixed mechanisms comprising at least a thermal random degradation with subsequent auto-accelerated transesterification, and a kinetically favored chain reaction from crotonate chain ends. The thermal degradation behavior of PHB varied with changes in time and/or temperature. From the kinetic analysis of changes in molecular weight, it was found that a non-auto-catalytic random degradation proceeding in the initial period was followed by an auto-accelerated reaction in the middle period. From the kinetic analysis of weight loss behavior, it is proposed that there are some kinetically favored scissions occurring at the chain ends, where the degradation proceeded by a 0th-order weight loss process in the middle stage. The observed 0th-order weight loss process was assumed to be an unzipping reaction occurring at ester groups neighboring the crotonate end groups.