The effectiveness of the reactive extrusion technique was investigated for poly(ethylene terephthalate) to promote the concept of closed-loop recycling, that is, the reuse of waste material in the initial application. More specifically, a chain-extender system, consisting of pyromellitic dianhydride, polyol, and a catalyst, was employed, and its efficiency regarding the improvement of the recyclate quality was evaluated. Accordingly, rheological and thermal characterizations were performed and used as criteria of the modification induced in the polymer molecular structure during processing due to the counteracting degradation and chain-extension reactions. In particular, the molecular weight, related to intrinsic viscosity and melt flow rate measurements, of modified poly(ethylene terephthalate) samples was found to increase with the additive content. Simultaneously, a decrease in the crystallinity was observed, attributed to the branching effect of the chain extender, which restricted the ability of the macromolecules to organize in the crystal structure. Beyond a critical concentration of the additive system, the molecular weight of the treated samples started to decrease again, and this was accompanied by a small increase in the crystallinity. (c) 2007 Wiley Periodicals, Inc.