SynopsisThe effect of a series of transition metal (Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn) stearates on the photodegradation of a high-density polyethylene was examined mainly by changes in the carbonyl IR absorption of the sample films. Electron spin resonance (ESR) and luminescence spectra of the samples containing the copper stearate were measured. The photochemical reaction of the copper stearate was examined by IR and UV-visible spectroscopies. The iron stearate was the most effective a t an early stage of the photodegradation of the polymer, and vanadium and manganese stearates accelerated it, while the copper stearate retarded it. The other metal stearates showed no applicable effect on the photodegradation. The relative intensity of the ESR spectra of the photoirradiated samples and that of the emission spectra of the unirradiated samples a t ca. 350 nm decreased with increasing concentration of the copper stearate. An absorption peak at 1580 cm-' decayed, and a new peak a t 1740 cm-' appeared with photoirradiation of the copper stearate. Absorption peaks of the copper stearate a t 252 and 665 nm decayed also rapidly with photoirradiation of the copper stearate in THF solution. The results suggest that one of the main retardative functions of the copper stearate in the photodegradation of polyethylene was an ultraviolet absorber.
The effect of triplet sensitizers, benzophenone and anthraquinone and metal acetylacetonates [Co(II, III), Cu, Sn, and Ni] on the photodegradation of polyurethane was examined. Ultravioletvisible (UV‐V) absorption spectra, gel formation, and luminescence emission of the polymer before and after irradiation were measured. Changes in UV‐V absorption of the polymer and the formation of an insoluble fraction in the polymer were accelerated in the presence of the triplet sensitizers, and (Co(II, III)), Cu, and Sn acetylacetonates. Unirradiated polyurethane was excited by irradiation at 290 and 346 nm, and emitted light at 310 and 420 nm. After 1/2 hr irradiation emission of luminescence was observed at 430 nm, excitation at 290 and 346 nm; after 2hr irradiation at 530 nm, excitation at 420 nm was observed. The results suggest that photodegradation of the polyurethane proceeds via excited triplet states forming excimer between the polymers at the initial stage and exciplexes between the polymer and degradation products or intermediates after a certain irradiation.
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