Hydrocarbon formation in the pyrolytic decomposition of methacrylate copolymers

A series of methyl methacrylate (MMA)–methacrylic acid (MAA) copolymers containing up to 50% methacrylic acid and the respective homopolymers were reproducibly pyrolyzed at 900°C and the fragments identified by gas chromatography (GC) or GC–mass spectroscopy. It was shown that PMMA and the MMA portions of blocky or random copolymers yielded 99% MMA, while a large portion (50–60%) of the MAA broke down to give a wide variety of hydrocarbons via decarboxylation and/or anhydride formation. Both unsaturated aliphatic and aromatic hydrocarbons, as well as the minor products of the MMA decomposition, support free‐radical processes for these decompositions. It was also shown that the copolymers readily complex oxygenated solvents (which did not affect decomposition) and metal ions (which markedly affected the products).