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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This work was partially supported by the Grants-in-Aid for Scientific Research (Nos. 21H04695 and 18H05515) from MEXT, Japan. We thank Dr Toshimichi Shibue (Materials Characterization Central Laboratory, Waseda University) for the solid-state NMR measurements. This work was the result of using research equipment (NMR spectrometer) in the Materials Characterization Central Laboratory of Waseda University, which was shared in the MEXT Project for promoting public utilization of advanced research infrastructure (program for supporting the construction of core facilities, Grant No. JPMXS0440500021).
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Watanabe, S., Saito, S., Hirai, M. et al. Synthesis of methylated phenylene sulfide polymers via bulk oxidative polymerization and their heat curing triggered by dynamic disulfide exchange. Polym J 54, 1–10 (2022). https://doi.org/10.1038/s41428-021-00557-0