The antioxidant role of α-tocopherol (vitamin E) in low-density polyethylene (LDPE), and the nature of its transformation products formed during extrusion of the polymer are investigated. The melt stabilizing effectiveness of α-tocopherol was found to be very high, higher than that of the commercial hindered phenol antioxidants, Irganox 1076 and 1010, after single and multiple extrusion. The high antioxidant activity of α-tocopherol as a melt stabilizer is due, at least in part, to its transformation products. The importance of the processing history and the parent antioxidant concentration on the transformation products is discussed. Transformation products of α-tocopherol were analyzed after each of the four extrusion passes of the polymer. These were fractionated, analyzed, and characterized by HPLC and spectroscopy, respectively. The main products formed are diastereoisomers of dimers and trimers, as well as aldehydes; the relative concentration of each was shown to depend on processing severity (number of extrusion passes) and the initial concentration of α-tocopherol. The dihydroxydimer was found to be formed at a high concentration relative to the other products and proportional with the initial concentration of tocopherol. Based on both the identity and distribution of transformation products, a mechanism is proposed for the melt stabilization effect of α-tocopherol in LDPE. © 1994 John Wiley & Sons, Inc.