The kinetics of the reaction between alkaline sulfides and halogenated aromatic monomers was studied using lithium sulfide and 4-chlorobenzophenone (1 a) and 4,4'-dichlorobenzophenone (1 b) as models. The release of H2S from reaction medium and the possible formation of a compound between sulfide and N-methyl-2-pyrrolidone (NMP) during the preliminary dehydration step are key steps of the reaction. The reaction proceeds following two successive kinetic regimes: a first one where rapid second-order reactions of sulfide and thiolate with 1 a or 1 b take place, and a second one where the slow release of sulfide from the compound formed during dehydration is rate determining and therefore governs the molecular weight of final polymer. A good agreement was found between theoretical curves calculated from this kinetic scheme and experimental data, indicating a polymerization mechanism based on an SNAr reaction mechanism.
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