Radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene in flow system, (9)

Seeded copolymerization of tetrafluoroethylene with propylene by radiation was carried out in a flow apparatus with pipe reactor at a pressure of 30 kg/cm2, a temperature of 400C, a dose rate of 4.9 x 105 rad/h, and at various monomer compositions. Polymer concentration in latex increases linearly at propylene fraction of 0.25 and accelerately at the fraction below 0.1 with reaction time. The polymerization rates are 36, 60, 57, and 46 g/h.l-H2O at propylene fractions of 0.01, 0.05, 0.1, and 0.25, respectively. Fluorine content of the polymer obtained at the end of polymerization is 53.8 wt% at propylene fractions of 0.25 and 0.1, and is 56.5 wt% at the fraction of 0.01. For the insoluble polymer in tetrahydrofuran produced at the fraction of 0.01, the fluorine content is 61.3 wt%. This indicates that monomer unit ratio of tetrafluoroethylene and propylene is 1.8/l. In the polymerization at a region of high tetrafluoroethylene content in monomer gas, it was elucidated that alternative arrangement of copolymer being characteristic in this system is broken down to produce tetrafluoroethylene rich polymer, and polymerization rate is reduced. This is explained by that addition of propylene monomer to tetrafluoroethylene polymer radical becomes rate-determining step due to the extremely poor propylene concentration in polymer particles. (author)