Thermal degradation processes in aliphatic polydithiocarbonates

The thermal degradation of three aliphatic polythiocarbonates was investigated by direct pyrolysis in the ion source of a mass spectrometer operating both in electron and chemical ionization modes. The overall evidence indicates that these polymers start decomposing at about 250–280°C by an end‐biting process initiating from the SH end‐groups, which produces a mixture of cyclic sulfides, disulfides, and dithiocarbonates. Another decomposition step is observed at higher temperature (ca. 350–370°C), producing essentially the same compounds evolved in the first stage, but with significant differences in their relative abundances. An intramolecular exchange (back‐biting) process is believed to be responsible for the second thermal decomposition stage