Chemical structures assigned for the low molecular weight fractions from degradation of poly(styrene sulfides)

A non-destructive analysis is performed of thermally unstable sulfur-styrene reaction products, combining preparative size exclusion chromatography (P-SEC), ultraviolet-visible (UV-vis) and nuclear magnetic resonance (NMR). The crystallizing compounds are identified as be 2,4-diphenylthiophanes with short sulfur bridge (x ∼ 2) contrary to earlier suggestions which were based on destructive analysis. A new cyclic structure (styrene polysulfide x = 1 up to 8) was assigned to the amorphous species containing a single styrene repeating unit. Comparison with the amorphous fractions suggests that the rigid ring of styrene repeating units in adjacent sequences is the characteristic feature for the crystallisability. The melting and crystallization behaviour of this crystalline component was observed, by optical microscopy (OM) and differential scanning calorimetry (DSC), to be step-wise as well as broad, due to the variation in the length of the sulfur bridge.