The products of the reaction of polyphenylene sulfide with SO3 and SOCl2

Two polymer fractions, respectively with 28–38% and 6–9% sulphonated (SO3H) phenylene rings, may be isolated in the solid-liquid reaction between p-polyphenylene sulfide and SO3 in refluxing dichloroethane-liquid SO2. The products relative yield depends on the experimental conditions of the reaction. No solvent has been found for these polymers. The reaction of the sulphonated polymers with SOCl2 leads to formation of higher substitution products containing both and functional groups. The polymers in chlorophenyl phenylsulphonylchloride form are soluble in excess SOCl2 and/or CHCl3, depending upon the concentration of ring chlorine. The mechanism of sulphonation in the heterogeneous medium and the presence of cross-links in the reaction products are discussed.