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The aim of this work is to investigate the degradation of low molar mass poly(ethylene terephthalate) (PET)/organically modified montmorillonite (OMMT) clay nanocomposites prepared by melt processing. The rheological behavior in combination with transmission electron microscopic images suggests an intercalation and therefore a percolating network. Furthermore, the results indicate that the increase of organoclay content caused a degradation of PET during processing of PET/OMMT nanocomposites, once it was observed the PET molar mass decreases. The effect mentioned could be attributed to an increase of Brønsted acidic sites on the platelet surface, which is produced by the Hofmann elimination reaction of ammonium, and also the presence of residual metal compounds on clay surface might possibly favored the polymer matrix degradation process.