Abstract
It was shown by IR spectroscopy that as a result of radiation at 80–100°K vinylene (−CH=CF− and vinylidene (>C=CF 2) double bonds are formed in polyvinylidene fluoride (PVF 2). A study was made of the relation between the formation of these double bonds and dose rate at different temperatures. From EPR spectra of oriented PVF 2 samples the formation of free alkyl fluoride radicals −CF− and −CF 2 was recorded. The formation of fluoro-vinylidene double bonds and terminal alkyl fluoride radicals proves that radiation breakdown occurs at the location of polymer chain branching and where monomer units are irregularly added to this chain. Absorption bands at 290 and 365 nm shown in electron spectra of PVF 2 irradiated at low temperature correspond to carbonium ions ▪ and fluorine anions F 2−, respectively. The band at 1590 cm −1 formed in the IR spectrum of PVF 2 irradiated at 80–100°K also corresponds to carbonium ions. Electron spectra show the formation of conjugate double bonds in irradiated PVF 2 and an elongation of the chain of conjugation as a result of heat developed in the sample irradiated. A hypothesis is suggested concerning the possibility of migration of the charge and the radical centre along the chain of PVF 2, which may explain features of radiation chemical processes taking place in this polymer.
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