Kinetics and mechanisms of polycondensation reactions between aryl halides and bisphenol A

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Abstract

Aryl chlorides (ArCl) or aryl fluorides (ArF) were used in polycondensation reactions to form poly(arylene ether sulfone)s (PAES). Interestingly, the kinetics of the ArF reaction fit a third-order rate law, which is attributed to the activation of the carbon-fluorine bond by two potassium cations (at least one bound to phenolate), which form a three-body complex. The ArCl monomer follows a second-order rate law, where a two-body complex forms at the initial state of the aromatic nucleophilic substitution (SNAr) pathway. These metal cation-activated complexes act as intermediates during the attack by the nucleophile. This finding was reproduced with either the potassium or the sodium counterion (introduced via potassium carbonate or sodium carbonate). Through a combination of experimental analysis of reaction kinetics and computational calculations with density functional theory (DFT) methods, the present work extends the fundamental understanding of polycondensation mechanisms for two aryl halides and highlights the importance of the CX-metal interaction(s) in the SNAr reaction, which is translational to other ion-activated substitution reactions. This journal is

Original languageEnglish (US)
Pages (from-to)5078-5087
Number of pages10
JournalPolymer Chemistry
Volume11
Issue number31
DOIs
StatePublished - Aug 21 2020

ASJC Scopus subject areas

  • Bioengineering
  • Biochemistry
  • Polymers and Plastics
  • Organic Chemistry

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