AbstractThis is the third in a series of papers in which the thermal degradation of ethylene‐vinyl acetate (EVA) and ethylene‐butyl acrylate (EBA) copolymers are compared. The EBA samples contained 0.8, 1.6, and 5.4 mol butyl acrylate (BA), respectively, and the EVA samples 1.2 and 6.7 mol vinyl acetate (VA). The samples were heated in nitrogen in a tubular oven at 285–390°C, for 6–120 min. The molecular weight distribution (MWD), long chain branching, and gel content were analyzed with size exclusion chromatography (SEC). The columns were connected to refractive index, viscometric, and light scattering detectors. EVA gave a pronounced molecular enlargement at all degradation temperatures. In EVA‐6.7, gel was formed at all degradation levels, whereas the low content sample, EVA‐1.2, did not form any visible amount of gel. The strong tendency to molecular enlargement is due to allyl radicals formed after thermal deacetylation and the formation of internal double bonds. These macroradicals will combine or, less frequently, add to double bonds. The EBA copolymers show a more polyethylenelike degradation behavior. At 285°C molecular enlargement dominates, but already at 333°C a net reduction in molecular size is observed. At high temperatures, ester pyrolysis of the BA groups give carboxylic groups and anhydrides. Alkaline treatment will not give any appreciable change in MWD, showing that the anhydride formation is mainly intramolecular. The chain scission increases with the BA content. This is probably due to β‐cleavage of tertiary macroradicals formed in the chain at the acrylate or carbo
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