ESR evidence for main‐chain scission produced by mechanical fracture of polymers at low temperature

ESR spectra have been observed from several polymers (polyethylene, polypropylene, polymethylmethacrylate, polytetrafluoroethylene, and polybutadiene) which were mechanically fractured in vacuum at 77°K. The spectra permit identification of the free radicals produced in chain scission. It has been demonstrated for the polymers of the type magnified image such as polypropylene and poly(methyl methacrylate), that the mechanical fracture produces two different scission radicals in pairs, namely, magnified image The results indicate convincingly that microscopic scission of polymer chains is caused by macroscopic destruction of polymeric material. The critical molecular size for mechanical rupture of polyethylene chains was experimentally determined to be a degree of polymerization between 70 and 100. This size agrees fairly well with the value predicted from a theoretical model.