聚丙烯/抗老化剂复合体系的γ-射线辐照降解研究

研究了聚丙烯(PP)及含有受阻酚类抗氧剂和受阻胺类光稳定剂复合体系的PP复合物经过γ-射线辐照后发生的结构变化及抗老化剂所起作用。实验利用红外光谱(FTIR)和示差扫描量热法(DSC)对PP的结构变化进行了系统表征。研究结果表明,当辐照剂量较小(50 kGy)时,纯PP及其复合物体系均未发生明显降解;当辐照剂量较大(≥50 kGy)时,PP及其复合物的羰基指数迅速提高,二者的结晶温度和熔融温度大幅度降低,说明PP发生了严重降解。在相同γ-射线辐照剂量条件下(≥50 kGy),PP复合物的羰基指数高于纯PP,而结晶温度以及熔融温度低于纯PP,表明高辐照剂量下抗老化剂复合物的存在不但没有阻止聚丙烯的降解,反而加快了降解的速率。

Investigation on degradation of polypropylene/stabilizers composites irradiated by gamma rays

The degradation behavior of polypropylene and polypropylene/stabilizer composites, caused by gamma radiation, was studied in the present work The stabilizers used were hindered phenol antioxidant and hindered amine light stabilizer. FTIR spectroscopy and DSC analysis were used to determine the structural variation induced by gamma radiation. It can be seen that the evolution of PP and composites PP/stabilizers on gamma irradiation is an increase in absorbance in the hydroxyl and carbonyl absorption regions. Carbonyl index calculated from FTIR spectra was used to characterize the rate of degradation. When the irradiation dose was small (<50 kGy), the degradation of pure polypropylene and polypropylene/stabilizers composites was not obvious; while the irradiation dose increased (> or =50 kGy), the carbonyl indexes of all the samples increased obviously, and the degradation degree of polypropylene/stabilizer composites was bigger than pure polypropylene. This result might be partially attributed to the molecular chain scission of hindered phenol and hindered amine under larger irradiation dose. The chain scission of stabilizers forms hydroperoxides and peroxide radicals, catalyzing the degradation of polypropylene. As the irradiation dose was small (<50 kGy), the crystallization temperatures of pure polypropylene and polypropylene/stabilizer composites all showed no remarkable changes; as the irradiation dose exceeded 50 kGy, the crystallization temperatures of pure polypropylene and polypropylene/stabilizer composites all decreased obviously. Correspondingly, the melting peaks of both pure polypropylene and polypropylene/stabilizer composites moved to lower temperature and split into two peaks with increasing the irradiation dose. The decrease of crystallization and melting temperatures might be attributed to the destruction of chemical structure and stereo-regularity of the molecular chain, due to the increasing of carbonyl and hydroxyl groups brought by the oxidation of polypropylene molecular chain. At the same irradiation dose (> or = 50 kGy), the crystallization and melting temperatures of polypropylene/stabilizer composites were lower than that of pure polypropylene. It indicates that the stabilizers accelerate the degradation of polypropylene. The results were accordant with the IR results.