Issue 31, 2017

Supramolecular polymer hydrogels induced by host–guest interactions with di-[cyclobis(paraquat-p-phenylene)] cross-linkers: from molecular complexation to viscoelastic properties

Abstract

Supramolecular polymer networks have been designed on the basis of a π-electron donor/acceptor complex: naphthalene (N)/cyclobis(paraquat-p-phenylene) (CBPQT4+ = B). For this purpose, a copolymer of N,N-dimethylacrylamide P(DMA-N1), lightly decorated with 1 mol% of naphthalene pendant groups, has been studied in semi-dilute un-entangled solution in the presence of di-CBPQT4+ (BB) crosslinker type molecules. While calorimetric experiments demonstrate the quantitative binding between N and B groups up to 60 °C, the introduction of BB crosslinkers into the polymer solution gives rise to gel formation above the overlap concentration. From a comprehensive investigation of viscoelastic properties, performed at different concentrations, host/guest stoichiometric ratios and temperatures, the supramolecular hydrogels are shown to follow a Maxwellian behavior with a strong correlation of the plateau modulus and the relaxation time with the effective amount of interchain cross-linkers and their dissociation dynamics, respectively. The calculation of the dissociation rate constant of the supramolecular complex, by extrapolation of the relaxation time of the network back to the beginning of the gel regime, is discussed in the framework of theoretical and experimental works on associating polymers.

Graphical abstract: Supramolecular polymer hydrogels induced by host–guest interactions with di-[cyclobis(paraquat-p-phenylene)] cross-linkers: from molecular complexation to viscoelastic properties

Supplementary files

Article information

Article type
Paper
Submitted
26 May 2017
Accepted
26 Jun 2017
First published
26 Jun 2017

Soft Matter, 2017,13, 5269-5282

Supramolecular polymer hydrogels induced by host–guest interactions with di-[cyclobis(paraquat-p-phenylene)] cross-linkers: from molecular complexation to viscoelastic properties

M. Fumagalli, K. Belal, H. Guo, F. Stoffelbach, G. Cooke, A. Marcellan, P. Woisel and D. Hourdet, Soft Matter, 2017, 13, 5269 DOI: 10.1039/C7SM01051F

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