Photooxidative and thermal degradation of polyethylenes: interrelationship by chemiluminescence, thermal gravimetric analysis and FTIR data

The thermal and photooxidative behaviour of polyethylenes of different manufacturing histories (linear low, metallocene and high density) have been investigated by FTIR spectroscopy and the data related to the chemiluminescence (CL) and thermal analysis of the polymers. The CL intensity and activation energies for thermal decomposition were found to be dependent on the rates of oxidation of the polymers under light and heat. On thermal oxidation, the activation energies were found to decrease with time and followed the order HDPE > m-PE > LLDPE, which correlated with the results obtained by means of CL analysis, where a higher intensity of CL at low temperature was found for HDPE. On photooxidation, the order followed their instability, i.e. m-PE > HDPE > LLDPE. The rates of thermal oxidation in each case were found to be the same irrespective of the nature of the oxidation product, i.e. hydroperoxide, vinyl and carbonyl groups. The influence of branching in the polymer appears to be important, showing a decrease of thermal stability as branching in polyethylene increases. © 2002 Elsevier Science B.V. All rights reserved.