Abstract
In recent years much evidence has been accumulated to implicate electronically excited oxygen (^1^Δ~g~) molecules as the agent responsible in photosensitized oxidations for the formation of allylic hydroperoxides from olefins and of endoperoxides from 1,3‐dienes. Little regarding the mechanistic aspects of the photo‐oxidative degradation of polybutadiene (PBD) is known, however. To determine if electronically excited oxygen (^1^Δ~g~) molecules can oxidize PBD, the ABS polyblend and standard samples of PBD's containing high trans, high cis, and high vinyl content were treated in homogeneous solution at low temperature with chemically produced singlet oxygen in situ. The source of the singlet oxygen was the triphenylphosphite‐ozone adduct. Studies by spectroscopy, elemental analysis, viscosity determinations, and gel measurements showed only the cis‐ and the trans‐PBD were susceptible to oxidation; no chain scission was involved in the attack of cis‐ and trans‐PBD by singlet oxygen; the oxidation of the cis PBD involved the initial formation of hydroperoxides which on thermal decomposition yielded gel. The trans‐PBD was found to oxidize but apparently by a mechanism different from that of cis‐PBD. Initial singlet oxygen attack of ABS proceeds by oxidation of the PBD portion of the polyblend. It was also observed that when only a small amount of the double bonds in the cis‐PBD polymer had been oxidized to hydroperoxides, subsequent thermal treatment of this sample resulted in gross structural changes in the whole polymer.