Fluorination of pressure-polymerized C60 phases

The reactivity of O-, T- and R-phases of the high pressure-high temperature (HPHT) polymerized C₆₀ towards gaseous fluorine in the temperature range of 50-250 °C was investigated. The reaction products were characterized by FTIR, powder X-ray diffraction, SEM, EDX, and VTP-EIMS to determine the bulk stoichiometries, bonding patterns, phase compositions, crystalline structures and thermal decomposition behavior of the fluorinated polymers. At 1 h isothermal treatment duration, fluorinated products with various bulk stoichiometries were obtained from different polymer phases with the R-phase showing the highest fluorine uptake. At 250 °C, all C₆₀ polymers showed partial decomposition to unfluorinated C₆₀ monomer under fluorine atmosphere. At 200 °C, the fluorination of R-phase yielded a pure fluoropolymer most likely having a {C₆₀F_x}_n (x = 36-44) composition. The same fluoropolymer was presumably obtained from O- and T-phases in lower yields. The linear chain structure was suggested for this new fluorocarbon polymer in agreement with the molecular mechanics modeling calculations.