Oxidative Metamorphosis of Poly(Styrenedisulfide) Backbone

This is the first report on the oxidation of a disulfide polymer, viz., poly(styrenedisulfide) (PSD). Oxidation was performed using $KMnO_4$ and $KHSO_4$, which are strong and mild oxidizing agents, respectively. Fourier transform-infrared spectroscopy (FT-IR) and intrinsic viscosity ([\eta]) measurements revealed that degradation of PSD occurs to some extent during oxidation when $KMnO_4$ was used. Further, FT-IR and [\eta] results indicated that the oxidation of PSD using $KMnO_4$ is better in heterogeneous conditions than under phase-transfer medium because the degradation was curtailed in the former case. Direct pyrolysis-mass spectrometry (DP-MS), Fast atom bombardment mass spectrometry (FABMS) and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) analyses of the oxidized PSD was carried out and the obtained results corroborate well with the FT-IR and [\eta] studies. Increased rigidity of the oxidized polymers which is reflected in their $T_g$ and [\eta] values, compared to PSD, was further confirmed by the radius of gyration $(R_g)$ and trans percentage data calculated from the molecular dynamics simulations studies