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

Abstract

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 C₂F₄ produces 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.