Mechanism of thermal degradation of poly(alkyl acrylate)s using pyrolysis gas chromatography mass spectrometry

The pyrolyses of homologous poly(alkyl acrylate)s is reported with identification of the major pyrolyses products. A mechanism involving random homolytic scission of the chain followed by a series of intermolecular and intramolecular transfer reactions has been proposed for poly(methyl acrylate) by Cameron and Kane and further developed by Haken, Ho, Houghton, and Gunawan. This mechanism is demonstrated to be generally applicable to the poly(n‐alkyl acrylate)s. Reaction mechanisms are postulated for the various products produced and ion fragmentation mechanisms for the mass spectra produced are shown.