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Terminal Flow of Cluster-Forming Supramolecular Polymer Networks: Single-Chain Relaxation or Micelle Reorganization?

Anton Mordvinkin1, Diana Döhler2, Wolfgang H. Binder2, Ralph H. Colby3, and Kay Saalwächter1,*

  • 1Institut für Physik–NMR, Martin-Luther-Universität Halle-Wittenberg, Betty-Heimann-Straße 7, 06120 Halle (Saale), Germany
  • 2Institut für Chemie–Makromolekulare Chemie, Martin-Luther-Universität Halle-Wittenberg, von-Danckelmann-Platz 4, 06120 Halle (Saale), Germany
  • 3Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, USA

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Phys. Rev. Lett. 125, 127801 – Published 17 September, 2020

DOI: https://doi.org/10.1103/PhysRevLett.125.127801

Abstract

We correlate the terminal relaxation of supramolecular polymer networks, based on unentangled telechelic poly(isobutylene) linear chains forming micellar end-group clusters, with the microscopic chain dynamics as probed by proton NMR. For a series of samples with increasing molecular weight, we find a quantitative agreement between the terminal relaxation times and their activation energies provided by rheology and NMR. This finding corroborates the validity of the transient-network model and the special case of the sticky Rouse model, and dismisses more dedicated approaches treating the terminal relaxation in terms of micellar rearrangements. Also, we confirm previous results showing reduction of the activation energy of supramolecular dissociation with increasing molecular weight and explain this trend with an increasing elastic penalty, as corroborated by small angle x-ray scattering data.

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Phys. Rev. Lett. 125, 127801– Published 17 September, 2020
  • Received 5 June 2020
  • Accepted 18 August 2020
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