Substituent groups of the diphenyl disulfides (DPSs) influence the cationic oxidative polymerization in the formation of polyphenylene sulfides (PPSs). A semiempirical MO calculation (AM1) was performed on the model compounds of PPS, such as thioanisoles (TAs) and diphenyl sulfides (PSs), in order to elucidate the reactivity of the cation. Linear PPS is formed on polymerization because of the high electron density of the carbon in the para position. The ratios of the frontier electron density of the carbon in the para position on the disulfide to the sulfur atom are ordered as follows; 3,5‐dimethyl‐PS>2,5‐dimethyl‐PS‐3‐methyl‐PS>nonsubstituted PS>2‐methyl‐PS>2,6‐dimethyl‐PS. The formation energies of the σ‐complex, which is the intermediate of the reaction, also shows the same order. The theoretical calculation indicates that 3,5‐dimethyl disubstituted disulfide and 3‐methyl one are most preferable monomers of this cationic oxidative polymerization.
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