Head‐to‐head polymers, 14. Thermal degradation of head‐to‐head and head‐to‐tail polystyrenes and poly(vinylcyclohexane)s

Abstract

AbstractThe thermal degradation behavior of head‐to‐head (H‐H) and head‐to‐tail (H‐T) polystyrenes and poly(vinylcyclohexane)s has been investigated by direct pyrolysis in a mass spectrometer. Both H‐H and H‐T isomers show only small differences in their initial temperatures of decomposition but remarkably different degradation processes. Whereas H‐T polystyrene decomposes in accordance with earlier investigations mainly by a radicalic depolymerization into the monomer and yields only a small amount of dimer and trimer, the H‐H polystyrene shows no unzipping and only a statistic degradation into oligomeric styrenes. The formation of stilbene is a diagnostic reaction of H‐H polystyrene. The pyrolysis‐mass spectra of H‐H and H‐T poly(vinylcyclohexane)s are more similar than those of the polystyrenes but the favored thermal cleavage between the two tertiary carbon atoms or next to the tertiary carbon atoms of the polymer backbone chain leads to some characteristic fragments, e.g. 1,3‐dicyclohexylpropene from the H‐T and 1,2‐dicyclohexylethane from the H‐H polymer.