Poly(2,5-dimethyl-1,4-phenylenesulfide) (PMPS) was prepared without halogenated compounds via oxygen oxidative polymerization of bis(2,5-dimethylphenyl) disulfide (2,5-DPS) with a VO(acac)2-strong acid catalyst under bulk conditions. The polymer showed crystalline features with a high melting temperature (Tm = 268 °C). After the subsequent heat curing of PMPS through the exchange reaction of a reactive disulfide bond, the polymer had a higher melting temperature (Tm = 286 °C), which was even higher than that of conventional poly(p-phenylene sulfide) (PPS) (Tm = 283 °C). Furthermore, the copolymerization of 2,5-DPS with diphenyl disulfide (DPS) led to products with higher crystallinities and melting temperatures owing to the increase in their molecular weights, which was derived from these products having higher solubilities in the monomer melt than PMPS.
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