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Kinetics of cross-linking and de-cross-linking of EPM rubber with thermoreversible Diels-Alder chemistry

Polgar, L. M., Kingma, A., Roelfs, M., van Essen, M., van Duin, M. & Picchioni, F., May-2017, In : European Polymer Journal. 90, p. 150-161 12 p.

Research output: Contribution to journalArticleAcademicpeer-review

  • L. M. Polgar
  • A. Kingma
  • M. Roelfs
  • M. van Essen
  • M. van Duin
  • F. Picchioni

The kinetics of the Diels-Alder (DA) cross-linking and retro-Diels-Alder (rDA) de-cross-linking reactions have been studied for furan-containing EPM rubber thermoversibly cross-linked with a bismaleimide. Cross-linking conversions obtained from spectroscopic methods deviate from rheological methods as the former take into consideration both the intermediate DA adduct and complete cross-links, while the latter only determine the formation and decomposition of complete cross-links. The thermoreversibility of the system was shown by a combination of equilibrium swelling and rheological measurements. Dynamic time sweeps of the rubber at different temperatures were used to determine the Arrhenius activation energies of 7.04 and 57.9 kJ/mol for the DA and the rDA reactions, respectively. Ea,DA is relatively low and suggests a diffusion limitation while Ea,rDA correspond to values reported in literature. Both values were used to simulate cross-link density profiles as a function of time and temperature that correspond well with the experimental data.

Original languageEnglish
Pages (from-to)150-161
Number of pages12
JournalEuropean Polymer Journal
Volume90
Publication statusPublished - May-2017

    Keywords

  • MALEATED ETHYLENE/PROPYLENE COPOLYMERS, COVALENT ADAPTABLE NETWORKS, GLASS-TRANSITION TEMPERATURE, BEARING FURAN MOIETIES, SOLID-STATE H-1-NMR, CLICK CHEMISTRY, CHAIN ENTANGLEMENTS, POLYMER NETWORKS, EPDM, VULCANIZATION

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