Polymerization of some fluorine-containing olefin oxides

The polymerization characteristics of six different fluorinated olefin oxides have been studied. The initial effort in this work was on the homopolymerization of 1,1,1‐trifluoro‐2,3‐butylene oxide. Attempts to polymerize this material have been made by mass polymerization over a broad temperature range using a number of different compounds as potential polymerization catalysts. Among these compounds were FeCl3, FeCl3 · 6H2O, AlCl3, a BF3‐etherate complex, KOH, gamma radiation from a cobalt‐60 source, a heterogeneous catalyst formed from aluminum triethyl and TiCl4, and a FeCl3‐propylene oxide complex. All of the polymeric products obtained from these experiments were liquids of a relatively low molecular weight. The highest molecular weight polymers were obtained using FeCl3, AlCl3, and BF3. An attempt was subsequently made to determine the relative polymerizability of other, more highly substituted, fluorinated olefin oxides. These were 1,1,1‐trifluoro‐2,3‐pentylene oxide, 1,1,1‐trifluoro‐2,3‐isopentylene oxide, 1,1,1,2,2,3,3‐heptafluoro‐4,5‐hexylene oxide, 1,1,1,‐2,2,3,3‐heptafluoro‐4,5‐heptylene oxide, and 1,1,1,2,2,3,3‐heptafluoro‐4,5‐isoheptylene oxide. FeCl3 and AlCl3 were found to be effective catalysts for the mass polymerization of these materials to form liquid polymers. It was observed that the tendency to polymerize decreases in this group of compounds as the amount and complexity of substitution on the ethylene oxide nuclcus increases. All of these monomers are less reactive toward polymerization than is trifluorobutylene oxide; as a result, lower molecular weight products were formed in lower yields.