Polymerization of phenylacetylene with WOCl4/tetraphenyltin catalyst in benzene/1,4‐dioxane. Synthesis of high‐molecular‐weight poly(phenylacetylene)

Phenylacetylene was polymerized with WOCl4/tetraphenyltin (mole ratio 1:2) catalyst in benzene and benzene/1,4‐dioxane mixtures. The resulting polymers were characterized by means of multidetector size‐exclusion chromatography and 1H NMR and IR spectroscopy. 1,4‐Dioxane used as a co‐solvent was found to increase both the content of cis units and the molecular weight of poly(phenylacetylene) (PPhA); a weight‐average molecular weight of M̄w = 1 · 106 was reached. In spite of the high mole ration monomer: catalyst (1260:1) used in the polymerizations high yields of PPhA were attained. No effect of an alteration in PPhA microstructure upon its degradation in tetrahydrofuran solution exposed to air has been observed.