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Issue 31, 2020

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

Author affiliations

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.

Graphical abstract: Kinetics and mechanisms of polycondensation reactions between aryl halides and bisphenol A

Supplementary files

Article information


Submitted
20 May 2020
Accepted
08 Jul 2020
First published
09 Jul 2020

Polym. Chem., 2020,11, 5078-5087
Article type
Paper
Author version available

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

Y. Yang, C. L. Muhich and M. D. Green, Polym. Chem., 2020, 11, 5078 DOI: 10.1039/D0PY00740D

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