Associating polymers constitute a fascinating class of materials because of the richness in their rheological behavior. Their rheology is known to be mainly dictated by the nature and intrinsic stabilities of transient associations. Here, we provide a direct observation of the importance of free associating sites in the macroscopic relaxation of supramolecular networks constructed from ultrahigh molecular weight polymers with sparsely distributed stickers of finite functionality. Their rheological signature affords evidence that the macroscopic relaxation of supramolecular networks can be apparently dissociated from the intrinsic lifetime of the associating units, provided that diffusion processes do not lead to successful chain relaxation at the microscopic level.
References
1.
Leibler
, L.
, M.
Rubinstein
, and R. H.
Colby
, “Dynamics of reversible networks
,” Macromolecules
24
, 4701
–4707
(1991
).2.
Rubinstein
, M.
, and A. N.
Semenov
, “Dynamics of entangled solutions of associating polymers
,” Macromolecules
34
, 1058
–1068
(2001
).3.
Rubinstein
, M.
, and A. V.
Dobrynin
, “Solutions of associative polymers
,” Trends Polym. Sci.
5
, 181
–186
(1997
).4.
Winnik
, M. A.
, and A.
Yekta
, “Associative polymers in aqueous solution
,” Curr. Opin. Colloid Interface Sci.
2
, 424
–436
(1997
).5.
Yu
, G.
, X.
Yan
, C.
Han
, and F.
Huang
, “Characterization of supramolecular gels
,” Chem. Soc. Rev.
42
, 6697
–6722
(2013
).6.
Herbst
, F.
, D.
Döhler
, P.
Michael
, and W. H.
Binder
, “Self-healing polymers via supramolecular forces
,” Macromol. Rapid Commun.
34
, 203
–220
(2013
).7.
Seiffert
, S.
, and J.
Sprakel
, “Physical chemistry of supramolecular polymer networks
,” Chem. Soc. Rev.
41
, 909
–930
(2012
).8.
Baxandall
, L.
, “Dynamics of reversibly crosslinked chains
,” Macromolecules
22
, 1982
–1988
(1989
).9.
Marrucci
, G.
, S.
Bhargava
, and S.
Cooper
, “Models of shear-thickening behavior in physically cross-linked networks
,” Macromolecules
26
, 6483
–6488
(1993
).10.
Semenov
, A. N.
, and M.
Rubinstein
, “Thermoreversible gelation in solutions of associative polymers. 1. Statics
,” Macromolecules
31
, 1373
–1385
(1998
).11.
Semenov
, A.
, and M.
Rubinstein
, “Dynamics of entangled associating polymers with large aggregates
,” Macromolecules
35
, 4821
–4837
(2002
).12.
Ahmadi
, M.
, L. G. D.
Hawke
, H.
Goldansaz
, and E.
van Ruymbeke
, “Dynamics of entangled linear supramolecular chains with sticky side groups: Influence of hindered fluctuations
,” Macromolecules
48
, 7300
–7310
(2015
).13.
Amin
, D.
, A. E.
Likhtman
, and Z.
Wang
, “Dynamics in supramolecular polymer networks formed by associating telechelic chains
,” Macromolecules
49
, 7510
–7524
(2016
).14.
Hawke
, L.
, M.
Ahmadi
, H.
Goldansaz
, and E.
Van Ruymbeke
, “Viscoelastic properties of linear associating poly(n-butyl acrylate) chains
,” J. Rheol.
60
, 297
–310
(2016
).15.
Ianniruberto
, G.
, and G.
Marrucci
, “New interpretation of shear thickening in telechelic associating polymers
,” Macromolecules
48
, 5439
–5449
(2015
).16.
Tripathi
, A.
, K. C.
Tam
, and G. H.
McKinley
, “Rheology and dynamics of associative polymers in shear and extension: Theory and experiments
,” Macromolecules
39
, 1981
–1999
(2006
).17.
Watanabe
, H.
, Y.
Matsumiya
, Y.
Masubuchi
, O.
Urakawa
, and T.
Inoue
, “Viscoelastic relaxation of Rouse chains undergoing head-to-head association and dissociation: Motional coupling through chemical equilibrium
,” Macromolecules
48
, 3014
–3030
(2015
).18.
Boudara
, V. A.
, and D. J.
Read
, “Stochastic and preaveraged nonlinear rheology models for entangled telechelic star polymers
,” J. Rheol.
61
, 339
–362
(2017
).19.
Rubinstein
, M.
, and A. N.
Semenov
, “Thermoreversible gelation in solutions of associating polymers. 2. Linear dynamics
,” Macromolecules
31
, 1386
–1397
(1998
).20.
Stukalin
, E. B.
, L.-H.
Cai
, N. A.
Kumar
, L.
Leibler
, and M.
Rubinstein
, “Self-healing of unentangled polymer networks with reversible bonds
,” Macromolecules
46
, 7525
–7541
(2013
).21.
Gold
, B. J.
, C. H.
Hövelmann
, N.
Lühmann
, N. K.
Székely
, W.
Pyckhout-Hintzen
, A.
Wischnewski
, and D.
Richter
, “Importance of compact random walks for the rheology of transient networks
,” ACS Macro Lett.
6
, 73
–77
(2017
).22.
Hackelbusch
, S.
, T.
Rossow
, P.
van Assenbergh
, and S.
Seiffert
, “Chain dynamics in supramolecular polymer networks
,” Macromolecules
46
, 6273
–6286
(2013
).23.
Perrier
, S.
, and P.
Takolpuckdee
, “Macromolecular design via reversible addition-fragmentation chain transfer (RAFT)/xanthates (MADIX) polymerization
,” J. Polym. Sci., Part A: Polym. Chem.
43
, 5347
–5393
(2005
).24.
Moad
, G.
, J.
Chiefari
, J.
Krstina
, R. T. A.
Mayadunne
, A.
Postma
, E.
Rizzardo
, and S. H.
Thang
, “Living free radical polymerization with reversible addition-fragmentation chain transfer (the life of RAFT)
,” Polym. Int.
49
, 993
–1001
(2000
).25.
Read
, E.
, A.
Guinaudeau
, D. J.
Wilson
, A.
Cadix
, F.
Violleau
, and M.
Destarac
, “Low temperature RAFT/MADIX gel polymerisation: Access to controlled ultra-high molar mass polyacrylamides
,” Polym. Chem.
5
, 2202
–2207
(2014
).26.
Wilson
, D. J.
, J.
Brassinne
, A.
Cadix
, and J.-C.
Castaing
, France patent pending (2 December 2016
).27.
Jongschaap
, R.
, R.
Wientjes
, M.
Duits
, and J.
Mellema
, “A generalized transient network model for associative polymer networks
,” Macromolecules
34
, 1031
–1038
(2001
).28.
Rubinstein
, M.
, and A. V.
Dobrynin
, “Associations leading to formation of reversible networks and gels
,” Curr. Opin. Colloid Interface Sci.
4
, 83
–87
(1999
).29.
Rossow
, T.
, A.
Habicht
, and S.
Seiffert
, “Relaxation and dynamics in transient polymer model networks
,” Macromolecules
47
, 6473
–6482
(2014
).30.
Indei
, T.
, T.
Koga
, and F.
Tanaka
, “Theory of shear-thickening in transient networks of associating polymers
,” Macromol. Rapid Commun.
26
, 701
–706
(2005
).31.
Xu
, D. H.
, L. L.
Hawk
, D. M.
Loveless
, S. L.
Jeon
, and S. L.
Craig
, “Mechanism of shear thickening in reversibly cross-linked supramolecular polymer networks
,” Macromolecules
43
, 3556
–3565
(2010
).32.
Xu
, D.
, and S. L.
Craig
, “Strain hardening and strain softening of reversibly cross-linked supramolecular polymer networks
,” Macromolecules
44
, 7478
–7488
(2011
).33.
Kim
, S. H.
, H. G.
Sim
, K. H.
Ahn
, and S. J.
Lee
, “Large amplitude oscillatory shear behavior of the network model for associating polymeric systems
,” Korea-Aust. Rheol. J.
14
, 49
–55
(2002
).34.
Sim
, H. G.
, K. H.
Ahn
, and S. J.
Lee
, “Large amplitude oscillatory shear behavior of complex fluids investigated by a network model: A guideline for classification
,” J. Non-Newtonian Fluid Mech.
112
, 237
–250
(2003
).35.
Tapadia
, P.
, S.
Ravindranath
, and S.-Q.
Wang
, “Banding in entangled polymer fluids under oscillatory shearing
,” Phys. Rev. Lett.
96
, 196001
(2006
).36.
Olmsted
, P. D.
, “Perspectives on shear banding in complex fluids
,” Rheol. Acta
47
, 283
–300
(2008
).37.
Graham
, M. D.
, “Wall slip and the nonlinear dynamics of large amplitude oscillatory shear flows
,” J. Rheol.
39
, 697
–712
(1995
).38.
Larson
, R. G.
, “Instabilities in viscoelastic flows
,” Rheol. Acta
31
, 213
–263
(1992
).39.
Groisman
, A.
, and V.
Steinberg
, “Elastic turbulence in a polymer solution flow
,” Nature
405
, 53
–55
(2000
).40.
Atalık
, K.
, and R.
Keunings
, “On the occurrence of even harmonics in the shear stress response of viscoelastic fluids in large amplitude oscillatory shear
,” J. Non-Newtonian Fluid Mech.
122
, 107
–116
(2004
).© 2017 The Society of Rheology.
2017
The Society of Rheology
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