Degradability of linear polyolefins under natural weathering

High density polyethylene (HDPE), linear low density polyethylene (LLDPE), and isotactic polypropylene (PP) containing antioxidant additives at low or zero levels were extruded and blown moulded as films. An HDPE/LLDPE commercial blend containing a pro-oxidant additive (i.e., an oxo-biodegradable blend) was taken from the market as supermarket bag. These four polyolefin samples were exposed to natural weathering for one year during which their structure and thermal and mechanical properties were monitored. This study shows that the real durability of olefin polymers may be much shorter than centuries, as in less than one year the mechanical properties of all samples decreased virtually to zero, as a consequence of severe oxidative degradation, that resulted in substantial reduction in molar mass accompanied by a significant increase in content of carbonyl groups. PP and the oxo-bio HDPE/LLDPE blend degraded very rapidly, whereas HDPE and LLDPE degraded more slowly, but significantly in a few months. The main factors influencing the degradability were the frequency of tertiary carbon atoms in the chain and the presence of a pro-oxidant additive. The primary (sterically hindered phenol) and secondary (phosphite) antioxidant additives added to PP slowed but did not prevent rapid photo-oxidative degradation, and in HDPE and LLDPE the secondary antioxidant additive had little influence on the rate of abiotic degradation at the concentrations used here.