Abstract
Structure and dynamics are examined for unentangled randomly-sulfonated polystyrene ionomer samples with cesium as counterion, using the X-ray scattering, DSC, and linear viscoelasticity (LVE) measurements. The large size of cesium cation leads to low association energy, enabling the dynamics to be examined for the high-ion-content samples, i.e., samples having a fraction of ionized monomers p up to 19%. X-ray scattering data shows an ionic peak, indicating the formation of ion aggregates. DSC reveals the glass transition process that shifts to higher T and broadens significantly when the ion content p is higher than 10%. In accordance with this broadening, the glassy and rubbery regimes seen in the LVE merge into one broad process with a wide relaxation distribution. We propose that the transition occurs when the number of ionic groups per chain becomes comparable to that of Kuhn segments per chain so that the polymer strands between ionic groups become non-flexible.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Arrese-Igor S, Alegría A, Colmenero J (2010) Comparison of calorimetric and dielectric single component glass transitions in PtBS-PI blends. Macromlecules 43:6406–6413. https://doi.org/10.1021/ma101022a
Baxandall LG (1989) Dynamics of reversibly cross-linked chains. Macromolecules 22:1982–1988. https://doi.org/10.1021/ma00194a076
Cao X, Yu X, Qin J, Chen Q (2019) Reversible gelation of entangled ionomers. Macromolecules 52:8771–8780. https://doi.org/10.1021/acs.macromol.9b01116
Castagna AM, Wang W, Winey KI, Runt J (2010) Influence of the degree of sulfonation on the structure and dynamics of sulfonated polystyrene copolymers. Macromolecules 43:10498–10504. https://doi.org/10.1021/ma102206f
Castagna AM, Wang W, Winey KI, Runt J (2011) Influence of cation type on structure and dynamics in sulfonated polystyrene ionomers. Macromolecules 44:5420–5426. https://doi.org/10.1021/ma2009657
Chen Q, Bao N, Wang J-HH, Tuniic T, Liang S, Colby RH (2015a) Linear viscoelasticity and dielectric spectroscopy of ionomer/plasticizer mixtures: a transition from ionomer to polyelectrolyte. Macromolecules 48:8240–8252. https://doi.org/10.1021/acs.macromol.5b01958
Chen Q, Huang C, Weiss RA, Colby RH (2015b) Viscoelasticity of reversible gelation for ionomers. Macromolecules 48:1221–1230. https://doi.org/10.1021/ma502280g
Chen Q, Liang S, Shiau H-S, Colby RH (2013a) Linear viscoelastic and dielectric properties of phosphonium siloxane ionomers. ACS Macro Lett 2:970–974. https://doi.org/10.1021/mz400476w
Chen Q, Tudryn GJ, Colby RH (2013b) Ionomer dynamics and the sticky rouse model. J Rheol 57:1441–1462. https://doi.org/10.1122/1.4818868
Chu B, Wu DQ, Lundberg RD, MacKnight WJ (1993) Small-angle x-ray scattering (SAXS) studies of sulfonated polystyrene ionomers. 1 Anomalous SAXS. Macromolecules 26:994–999. https://doi.org/10.1021/ma00057a018
Chu B et al (1988) Synchrotron small-angle X-ray-scattering of sulfonated polystyrene ionomers. Macromolecules 21:523–525. https://doi.org/10.1021/Ma00180a043
Colby RH et al (1998) Dynamics of lightly sulfonated polystyrene ionomers. Phys Rev Lett 81:3876–3879. https://doi.org/10.1103/PhysRevLett.81.3876
Earnest TR, Higgins JS, Handlin DL, Macknight WJ (1981) Small-angle neutron-scattering from sulfonate ionomers. Macromolecules 14:192–196. https://doi.org/10.1021/Ma50002a040
Eisenberg A, Hird B, Moore RB (1990) A new multiplet-cluster model for the morphology of random ionomers. Macromolecules 23:4098–4107. https://doi.org/10.1021/ma00220a012
Eisenberg A, Kim J-S (1998) Introduction to ionomers. Wiley, New York
Fetters LJ, Lohse DJ, Colby RH (2007a) Chain dimensions and entanglement spacings. In: Mark JE (ed) Physical Properties of Polymers Handbook. Springer, New York, New York, pp 447–454. https://doi.org/10.1007/978-0-387-69002-5_25
Fetters LJ, Lohse DJ, Colby RH (2007b) Chain dimensions and entanglement spacings. In: Mark JE (ed) Physical Properties of Polymers Handbook, 2nd edn. Springer, New York, pp 445–452
Green MS, Tobolsky AV (1946) A new approach to the theory of relaxing polymeric media. J Chem Phys 14:80–92. https://doi.org/10.1063/1.1724109
Huang C, Chen Q, Weiss RA (2017) Rheological behavior of partially neutralized oligomeric sulfonated polystyrene ionomers. Macromolecules 50:424–431. https://doi.org/10.1021/acs.macromol.6b02423
Kim J-S, Jackman RJ, Eisenberg A (1994) Filler and percolation behavior of ionic aggregates in styrene-sodium methacrylate ionomers. Macromolecules 27:2789–2803. https://doi.org/10.1021/ma00088a021
Kim S-H, Kim J-S (2003a) Effects of low matrix glass transition temperature on the cluster formation of ionomers having two ion pairs per ionic repeat unit. Macromolecules 36:1870–1875. https://doi.org/10.1021/ma021502v
Kim S-H, Kim J-S (2003b) Relationships between the glass transition temperatures and the type of cations in poly(ethyl acrylate) ionomers. Macromolecules 36:2382–2386. https://doi.org/10.1021/ma021744v
Kim S-H, Kim J-S (2003c) Relationships between the glass transition temperatures and the type of cations in poly(ethyl acrylate) ionomers. Macromolecules 36:2382–2386. https://doi.org/10.1021/ma021744v
Lantman CW, Macknight WJ, Lundberg RD (1989) Structural-properties of ionomers. Annu Rev Mater Sci 19:295–317. https://doi.org/10.1146/annurev.ms.19.080189.001455
Lefelar JA, Weiss RA (1984) Concentration and counterion dependence of cluster formation in sulfonated polystyrene. Macromolecules 17:1145–1148. https://doi.org/10.1021/ma00136a007
Leibler L, Rubinstein M, Colby RH (1991) Dynamics of reversible networks. Macromolecules 24:4701–4707. https://doi.org/10.1021/ma00016a034
Liang S et al (2014) High ion content siloxane phosphonium ionomers with very low Tg. Macromolecules 47:4428–4437. https://doi.org/10.1021/ma5001546
Ling GH, Wang Y, Weiss RA (2012) Linear Viscoelastic and Uniaxial Extensional Rheology of Alkali Metal Neutralized Sulfonated Oligostyrene Ionomer Melts. Macromolecules 45:481–490. https://doi.org/10.1021/ma201854w
Liu S, Wu S, Chen Q (2020) Using coupling motion of connecting ions in designing telechelic ionomers. ACS Macro Lett 9:917–923. https://doi.org/10.1021/acsmacrolett.0c00256
Nishida M, Eisenberg A (1996) Dynamic mechanical study of sodium sulfonated random ionomers based on hydrogenated styrene-butadiene copolymer. Macromolecules 29:1507–1515. https://doi.org/10.1021/ma9513630
Register RA, Cooper SL (1990) Anomalous small-angle x-ray scattering from nickel-neutralized ionomers. 1 Amorphous polymer matrixes. Macromolecules 23:310–317. https://doi.org/10.1021/ma00203a053
Rubinstein M, Semenov AN (1998) Thermoreversible gelation in solutions of associating polymers. 2 Linear Dynamics. Macromolecules 31:1386–1397. https://doi.org/10.1021/ma970617+
Stadler FJ, Pyckhout-Hintzen W, Schumers J-M, Fustin C-A, Gohy J-F, Bailly C (2009) Linear viscoelastic rheology of moderately entangled telechelic polybutadiene temporary networks. Macromolecules 42:6181–6192. https://doi.org/10.1021/ma802488a
Visser SA, Pruckmayr G, Cooper SL (1991) Small-angle neutron scattering analysis of model polyurethane ionomers. Macromolecules 24:6769–6775. https://doi.org/10.1021/ma00025a033
Wang WQ (2010) Morphology of ion-containing polymers: correlations between structure, dynamics, and ion conduction. University of Pennsylvania
Weiss RA, Lefelar JA (1986) The influence of thermal history on the small-angle x-ray-scattering of sulfonated polystyrene ionomers. Polymer 27:3–10. https://doi.org/10.1016/0032-3861(86)90349-6
Weiss RA, Zhao HY (2009) Rheological behavior of oligomeric ionomers. J Rheol 53:191–213. https://doi.org/10.1122/1.3003570
Wollmann D, Williams CE, Eisenberg A (1992) Aggregate modification via plasticization of ionomers-dynamic mechanical and morphological studies. Macromolecules 25:6775–6783. https://doi.org/10.1021/ma00051a009
Wu S, Liu S, Zhang Z, Chen Q (2019) Dynamics of telechelic ionomers with distribution of number of ionic stickers at chain ends. Macromolecules 52:2265–2276. https://doi.org/10.1021/acs.macromol.8b01776
Zhang LH, Brostowitz NR, Cavicchi KA, Weiss RA (2014) Perspective: ionomer research and applications. Macromol React Eng 8:81–99. https://doi.org/10.1002/mren.201300181
Zhang Z, Huang C, Weiss R, Chen Q (2017a) Association energy in strongly associative polymers 61:1199–1207. https://doi.org/10.1122/1.4997586
Zhang Z, Liu C, Cao X, Wang J-HH, Chen Q, Colby RH (2017b) Morphological evolution of ionomer/plasticizer mixtures during a transition from ionomer to polyelectrolyte. Macromolecules 50:963–971. https://doi.org/10.1021/acs.macromol.6b02225
Acknowledgments
QC acknowledges the National Natural Science Foundation of China (21722407 and 21674117). We thank Prof. Wensheng Xu for the insightful discussion.
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Yu, X., Cao, X. & Chen, Q. Rheological properties of sulfonated polystyrene ionomers at high-ion contents. Rheol Acta 60, 241–249 (2021). https://doi.org/10.1007/s00397-021-01265-5
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00397-021-01265-5