Activation of the hydrolytic polymerization of ε-caprolactam by ester functions: Straightforward route to aliphatic polyesteramides

Gaëlle Deshayes, Cécile Delcourt, Ingrid Verbruggen, Lise Trouillet-Fonti, Franck Touraud, Etienne Fleury, Philippe Degée, Mathias Destarac, Rudolph Willem, Philippe Dubois

Research output: Contribution to journalArticlepeer-review

Abstract

The hydrolytic polymerization of ε-caprolactam (CLa) was carried out in bulk (in absence of solvent) at 250 °C in the presence of carboxylic esters and aqueous H3PO2. It turned out that by conducting the ring opening polymerization (ROP) of CLa in the presence of PEO-C(O)-O-C5H11, a selected model ester (PEO = poly(ethylene oxide)), a remarkable activating effect of the ester function on the hydrolytic polymerization of the lactam was observed yielding PEO-b-PCLa diblock copolymers. The comparison of the CLa monomer conversions obtained with or without the model ester activated by H3PO2, as determined by 1H NMR spectroscopy, has enabled to propose a multi-step mechanism in which three major reactions occurred: (i) ester and lactam hydrolysis, (ii) aminolysis of the carboxylic ester by the resulting primary amine of the hydrolyzed/opened lactam ring and (iii) condensation reactions between carboxylic acids and both amine/hydroxyl functions. The overall result of this multi-step mechanism can be assimilated as an "insertion" of the opened lactam into the ester function. By conducting the hydrolytic polymerization of CLa in the presence of an aliphatic polyester chain, such as poly(ε-caprolactone) (PCLo), polyesteramides were recovered with high yields and random distributions of the CLa and CLo repetitive units as determined by 13C NMR.

Original languageEnglish
Pages (from-to)1392-1407
Number of pages16
JournalReactive and Functional Polymers
Volume68
Issue number9
DOIs
Publication statusPublished - 1 Sep 2008
Externally publishedYes

Keywords

  • ε-Caprolactam
  • Hydrolytic polymerization
  • Polyamide
  • Polyesteramides
  • Ring-opening polymerization

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