Ionic products in ground polymer. IV. Anions in poly(vinylidene fluoride)

When poly(vinylidene fluoride) (PVDF) was ground with tetracyanoethylene (TCNE) powder in a vibration glass ball mill in vacuum in the dark at 77 K, the TCNE anion radical (TCNE‐) was detected in the mixture by ESR spectroscopy. The TCNE.‐ is formed by the ion of electrons by TCNE from the anion that is produced by a heterogeneous bond scission of carbon‐carbon bonds in the polymer main chain. The assignment of TCNE.‐ was carried out by the ESR spectral simulation on the basis of an anisotropic effective hyperfine tensor that includes a forbidden transition term. At least 85% of the bond scission of the PVDF main chain is induced by a heterogeneous process to produce ionic products. The yield of these mechanions seems to increase with the polarity of carbon‐carbon bond owing to a substituent group bonded to the carbon in the polymer main chain.