Infrared spectrophotometric studies on polyethylene. II. Oxidation

Abstract

Polyethylene can be heat‐oxidized in air when temperatures in excess of 125°C. are employed or photo‐oxidized when exposed to ultraviolet radiation during weathering. Infrared spectrophotometric studies show that during these types of oxidation carbonyl groups are formed and the concentrations of the three types of carbon to carbon double bond groups present are altered. Grating spectra in the 5.6–6.0 micron region reveal that the carbonyl groups formed by heat‐oxidation are mainly ketonic (5.81 microns) although some aldehyde (5.77 microns) and acid (5.84 microns) groups are also present. In photo‐oxidized samples, the carbonyl groups are rather well distributed among the aldehyde, acid and ketone forms. For oxidized samples showing intense carbonyl absorptions, there is a small increase in the concentration of RHCCHR groups (10.35 microns) for both types of oxidation. At this same degree of oxidation both the heat‐and photo‐oxidized samples show decreases in the concentration of RRCCH 2 groups (11.25 microns). However, this decrease is considerably more pronounced in the photo‐oxidized samples. Finally, there is a small decrease in the concentration of RHCCH 2 groups (10.07 and 11.00 microns) in the heat‐oxidized samples which stands in contrast to a large increase in concentration of RHCCH 2 groups produced by photo‐oxidation. The presence of an absorption maximum at 2.81 microns as the heat‐oxidation of polyethylene is occuring is indicative of unstable hydroperoxide groups.