Vinylene carbonate oxidation potential

Comparison of the common electrolyte solvents (EC, propylene carbcaiate [PC], dimethyl carbonate [DMC], EMC, vinylene carbonate [VC], dimethoxyethane [DME]) oxidative stability with experiments was reported by Zhang et al. [3]. While trends of the oxidative stability were reasonably captured in this study, typical deviations between experiments and simulations were reported to be around 0.5-1.0 V. Note that Zhang et al. [3] did not use the value of 1.4 V to convert from the absolute to Li /Li potential scale, instead they used the Li/LF and M/M" cycles with a number of calculated/estimated quantities, resulting in the absolute potential versus LF/Li being around 2.2 V. Application of the value of 1.4 or 1.54 V derived from SHE potential in water and acetonitrile and using the standard LF/Li vs. SHE potential will result in an improved agreement between QC-based values reported by Zhang et al. [3] and experiments. 

In polyethylene, the tertiary carbon atom, which dominated the chemistry of the oxidative degradation of PP, is present only at branch points. This suggests that there may be a difference among LDPE, LLDPE and HDPE in terms of the expected rates of oxidation. This is complicated further by the presence of catalyst residues from the Ziegler-Natta polymerization of HDPE that may be potential free-radical initiators. The polymers also have differences in degree of crystallinity, but these should not impinge on the melt properties at other than low temperatures at which residual structure may prevail in the melt. Also of significance is residual unsaturation such as in-chain tra s-vinylene and vinylidene as well as terminal vinyl, which are defects in the idealized PE strucmre. 

---