Effect of Supramolecular Interchain Sticking on the Low-Frequency Relaxation of Transient Polymer Networks.

Abstract

Supramolecular polymer networks and gels often exhibit three effects in rheology as a function of increasing strength and extent of transient chain interlinkage: (i) the longest relaxation time increases, (ii) the elastic part of the complex shear modulus on timescales longer than that increases, and (iii) the frequency-dependent power-law scaling of this modulus gets shallower in this regime. In a recent report, these effects have been systematically assessed by comparing transient polymer networks derived from a common precursor modified with different extents of a common hydrogen-bonding supramolecular sticker. In this communication, complementary studies are discussed that are based on a set of polymers also derived from a common precursor but all modified with the same extent (4.8%) of very different supramolecular crosslinking motifs. This comparison reveals that effect (iii) can be rationalized by exacerbation of polydispersity effects to the relaxation time spectrum if supramolecular interchain sticking is present. In addition, effect (ii) is addressable to a simple thermodynamic argument that appraises the supramolecular sticking contribution to the elastic part of the shear modulus in the relaxation regime.