Role of radicals, long-lived in a liquid, in the polymerization of fluoroolefins

Abstract

Using the polymerization of tetrafluoroethylene in a branched perfluoroolefin medium as an example (hexafluoropropylene, and its dimer and trimer), it is shown that hexafluoroethylene and its dimer are effective traps for growing polymer radicals. As a result of this interaction inactive, long-lived radicals not capable of mutual recombination are formed, which results in chain termination and prevents homo- and copolymerization of hexafluoropropylene. The hexafluoropropylene trimer is unable to add any radical apart from atomic fluorine and is an almost inert medium in the radical processes under consideration.