Radiation-induced polymerization at high pressure of cis- and trans-1,3,3,3-tetrafluoropropene in bulk and with tetrafluoroethylene

The radiation-induced polymerization of cis- and trans-1,3,3,3-tetrafluoropropene in bulk and with tetrafluoroethylene was studied at pressures between 5000 and 15000 atm and temperatures between 21 and 100°C. At 10³ rad/hr the homopolymerization rates range from about 10^?4 to 1%/hr. The activation enthalpy and volume are about 8 kcal/mole (33 kJ/mole) and ?10 cm³/mole, respectively, for both isomers. The cis isomer polymerizes about twice as rapidly as the trans isomer. The latter freezes in the experimental range of temperature and pressure; the polymerization rate is very low in solid phase. Polymer intrinsic viscosities increase with polymerization pressure and decrease with polymerization temperature; the largest value obtained was 0.23 dl/g. In the copolymerizations all reactivity ratios favor incorporation of tetrafluoroethylene by factors of 6–16. The preference is stronger when the trans isomer is used.