Chain scission and mechanical degradation of polystyrene

The extent of molecular degradation of amorphous polystyrene when subjected to mechanical grinding at cryogenic temperature has been investigated using electron spin resonance, infrared spectroscopy, and viscometry. Essentially identical concentrations of chain ruptures in the degraded samples were found from infrared spectroscopic determinations of molecular end group concentrations and by the changes in the viscosity‐average molecular weights. The chain‐scission concentration was from two to four times the free‐radical concentrations, indicating that free‐radical‐propagation reactions play a much less dominant role in the degree of molecular damage associated with mechanically induced chain scission in glassy polymers. In addition, experiments were carried out as a function of molecular weight and these indicated a virtual independent behavior with molecular weight.