Polymers and telomers of perfluoro‐1,4‐pentadiene

Perfluoro‐1,4‐pentadiene was prepared by pyrolysis of sodium 3,5,6‐trichloroperfluorohexanoate and subsequent dehalogenation. The monomer was polymerized under a number of conditions of temperature and pressure using various periods and various dose rates of γ‐ray initiation. The compound was found to undergo doublebond migration producing perfluoro‐1,3‐pentadiene. The polymer samples, some of them rubbery, others grainy, are assumed to be copolymers of the 1,4‐pentadiene and the 1,3 pentadiene, the 1,4‐diene polymerizing according to a cyclic mechanism and the 1,3‐diene undergoing the 1,4‐addition that is characteristic of butadienes under certain conditions. Infrared and nuclear magnetic resonance studies tend to support these assumptions. Under polymerization conditions the monomer also produced four distinct dimers and traces of two monomeric substances.