Facile synthesis of telechelic poly(phenylene sulfide)s by means of electron-deficient aromatic sulfonium electrophiles

We report the facile synthesis of telechelic poly(phenylene sulfide) (PPS) derivatives bearing functional groups at both termini. α,ω-Dihalogenated dimethyl-substituted PPS were obtained in high yield with a high degree of end-functionalization by using soluble poly(2,6-dimethyl-1,4-phenylenesulfide) (PMPS) and 4,4′-dihalogenated diphenyl disulfide (X-DPS, X = Cl, Br) as a precursor and an end-capping agent, respectively. Further end-functionalization is achieved through cross-coupling reactions; particularly, the Kumada–Tamao cross-coupling reaction of bromo-terminated telechelic PMPS and a vinylated Grignard reagent afforded end-vinylated PMPS with thermosetting properties. This synthetic approach can be applied to the preparation of various aromatic telechelic polymers with the desired structures and functionalities.