Molecular Motion of the Junction Points in Model Networks Prepared by Acyclic Triene Metathesis

Macromolecular Rapid Communications
Lucas Caire da SilvaKenneth B Wagener

Abstract

The junction dynamics in a selectively deuterated model polymer network containing junctions on every 21st chain carbon is studied by solid state (2) H echo NMR. Polymer networks are prepared via acyclic triene metathesis of deuteron-labeled symmetric trienes with deuteron probes precisely placed at the alpha carbon relative to the junction point. The effect of decreasing the cross-link density on the junction dynamics is studied by introduction of polybutadiene chains in-between junctions. The networks are characterized by swelling, gel content, and solid state (1) H MAS NMR. Line shape analysis of the (2) H quadrupolar echo spectra reveals that the degree of motion anisotropy and the distribution of motion correlation times depend on the cross-link density and structural heterogeneity of the polymer networks. A detailed model of the junction dynamics at different temperatures is proposed and explained in terms of the intermolecular cooperativity in densely-packed systems.

References

Mar 14, 1988·Physical Review Letters·R OeserB Farago
Mar 14, 2013·Accounts of Chemical Research·Michael Ryan HansenHans Wolfgang Spiess

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