Anionic polymerization of hexafluoro-1,3-butadiene and characterization of the polymer

The present review describes the anionic polymerization of hexafluoro-1,3 -butadiene (HFBD) and the characterization of the polymer. HFBD which is hardly polymerized under radical polymerization conditions yielded the polymer with cesium and rubidium compounds as initiators in moderate conditions. X-ray photoelectron spectra and Raman spectra showed the structure of the polymer was similar to that of poly(hexafluoro-2-butyne). The polymerization mechanism, an addition reaction of the propagating anion to the 2-carbon of HFBD followed by isomerization of the propagating end group to yield the polyene structure, is proposed from the results of the investigation of initiation reaction and the structure of the polymers. Poly(HFBD) shows higher thermostability than poly(tetrafluoroethylene) in spite of bearing functional -CC-groups in the polymer main chain.