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Kinetics of the reaction between alkaline sulfides and aryl dichlorides — model study on 4‐chloro‐ and 4,4′‐dichlorobenzophenones
Author(s) -
Hedhli Lotfi,
Lesclingant Christelle,
Fradet Alain,
Maréchal Ernest
Publication year - 1997
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.1997.021980101
Subject(s) - chemistry , sulfide , kinetics , polymer chemistry , sodium sulfide , reaction mechanism , polymerization , monomer , order of reaction , aryl , reaction rate , polymer , inorganic chemistry , organic chemistry , reaction rate constant , catalysis , physics , alkyl , quantum mechanics
The kinetics of the reaction between alkaline sulfides and halogenated aromatic monomers was studied using lithium sulfide and 4‐chlorobenzophenone (1a) and 4,4′‐dichlorobenzophenone (1b) as models. The release of H 2 S 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 1a or 1b 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 S N Ar reaction mechanism.