The role of trifluoromethyl radicals in the radiation polymerization of gaseous tetrafluoroethylene.

Mass spectral analysis of the solid polymer produced by radiolysis of gaseous tetrafluoroethylene reveals significant initiation by CF3 species. In the presence of nitric oxide, CF3NO is produced [G(CF3NO) = 3.11] and polymerization is completely inhibited. The scavenging of CF3 radicals by NO in this system yields rate constant data consistent with available data for photochemically produced CF3 radicals. The mass spectrum of pure C2F4 contains a metastable peak, indicating that an ionic rearrangement of C2F4produces CF3+. Ion-molecule reactions producing CF3 ions and radicals can produce up to 1.17 per ion pair; the observed yield is 1.02 0.05. 3-Methylpentane, acting as a charge-transfer agent, inhibits polymerization.