| Abstract: | Bulk-crystallized isotactic polypropylene samples with different crystalline textures were etched by fuming nitric acid to remove the disordered region. The radicals produced by irradiation of γ-rays or ultraviolet light on these etched samples in vacuum at liquid nitrogen temperature were investigated by the ESR method. A triplet spectrum in addition to the original spectrum of polypropylene radicals was separated for the etched samples. It was concluded that this triplet was caused by radical species associated with nitro groups introduced on the surface of the crystalline residues by etching. The difference in the intensity of this triplet among the samples was ascribed to differences in crystalline textures and interpreted in a quantitative way. The concentration of polypropylene radicals corrected for the triplet differed among the quenched, annealed, and cold-drawn samples and the sample annealed one after drawing. This fact was interpreted on the basis of the hypothesis that radical sites were almost concentrated in the defects of crystal domain. The well known nonet spectrum, which can be observed at liquid nitrogen temperature after annealing the irradiated samples at room temperature, was also confirmed to be attributable to the defects of crystals. The behavior of free methyl radicals induced by ultraviolet irradiation was also found to be strongly dependent on the state of aggregation of the polymer molecules. |
