Issue 9, 2022

The role of transesterifications in reversible polycondensations and a reinvestigation of the Jacobson–Beckmann–Stockmayer experiments

Abstract

The polycondensations of adipic acid and 1,10-decanediol catalyzed by toluene sulfonic acid (TSA) were reinvestigated using MALDI TOF mass spectrometry and NMR spectroscopy. Unexpected reactions of TSA were detected along with incomplete conversion of the monomers. Furthermore, transesterification reactions of end-capped poly(1,10-decanediol adipate) and end-capped poly(ε-caprolactone) catalyzed by TSA were studied. Despite the quite different (ionic) reaction mechanisms, it was found that for polycondensations performed in bulk intermolecular transesterification is more efficient than the intramolecular “back-biting”; this scenario was not considered in the Jacobson–Stockmayer theory of reversible polycondensations. These results also confirm that the Jacobson–Stockmayer explanation of reversible polycondensations solely on the basis of ring chain equilibration is not only devoid of any experimental evidence, but also in contradiction to the results elaborated in this work.

Graphical abstract: The role of transesterifications in reversible polycondensations and a reinvestigation of the Jacobson–Beckmann–Stockmayer experiments

Supplementary files

Article information

Article type
Paper
Submitted
20 Dec 2021
Accepted
26 Jan 2022
First published
01 Feb 2022
This article is Open Access
Creative Commons BY-NC license

Polym. Chem., 2022,13, 1177-1185

The role of transesterifications in reversible polycondensations and a reinvestigation of the Jacobson–Beckmann–Stockmayer experiments

H. R. Kricheldorf, S. M. Weidner and J. Falkenhagen, Polym. Chem., 2022, 13, 1177 DOI: 10.1039/D1PY01679B

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