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Association and Relaxation of Supra-Macromolecular Polymers

Boothroyd, S.C.; Hoyle, D.M.; McLeish, T.C.B.; Munch, E.; Schach, R.; Smith, A.J.; Thompson, R.L.

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S.C. Boothroyd

D.M. Hoyle

T.C.B. McLeish

E. Munch

R. Schach

A.J. Smith


This paper describes the structures created by assembling functionalised entangled polymers and the effect these have on the rheology of the material. A polybutadiene (PBd) linear polymer precursor of sufficient molecular weight to be entangled is used. This is end functionalised with the self-associating group 2-ureido-4pyrimidinone (UPy). Interestingly, despite the relatively high molecular weight of the precursor diluting the UPy concentration, the effect on the material’s properties is significant. To characterise the assembled microstructure we present linear rheology, extensional non-linear rheology and small angle X-ray scattering (SAXS). The linear rheology shows that the functionalised PBd assembles into large macro-structures where the terminal relaxation time is up to seven orders of magnitude larger than the precursor. The non-linear rheology shows strain-hardening over a broad range of strain-rates. We then show by both SAXS and modelling of the extensional data that there must exist clusters of UPy associations and hence assembled polymers with branched architecture. By modelling the supra-molecular structure as an effective linear polymer, we show that this would be insufficient in predicting the strain-hardening behaviour at lower extension-rates. Therefore, in this flow regime the strain-hardening is likely to be caused by branching. This is backed up by SAXS measurements which show that UPy clusters larger than pair-pair groups exist.


Boothroyd, S., Hoyle, D., McLeish, T., Munch, E., Schach, R., Smith, A., & Thompson, R. (2019). Association and Relaxation of Supra-Macromolecular Polymers. Soft Matter, 15(26), 5296-5307.

Journal Article Type Article
Acceptance Date Jun 13, 2019
Online Publication Date Jun 14, 2019
Publication Date Jul 14, 2019
Deposit Date Jun 14, 2019
Publicly Available Date Jun 13, 2020
Journal Soft Matter
Print ISSN 1744-683X
Electronic ISSN 1744-6848
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 15
Issue 26
Pages 5296-5307


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