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Sulfonation of polystyrene: Toward the “ideal” polyelectrolyte

Authors

  • Jessica E. Coughlin,

    1. Department of Chemistry and Biochemistry, The Florida State University, Tallahassee, Florida
    Current affiliation:
    1. Jessica E. Coughlin, Department of Chemistry and Biochemistry, Center for Polymers and Organic Solids, University of California, Santa Barbara, California
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  • Andreas Reisch,

    1. Department of Chemistry and Biochemistry, The Florida State University, Tallahassee, Florida
    Current affiliation:
    1. Andreas Reisch, CNRS UMR 7213, Laboratoire de Biophotonique et Pharmacologie, Université de Strasbourg, Faculté de Pharmacie, France
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  • Marie Z. Markarian,

    1. Department of Chemistry and Biochemistry, The Florida State University, Tallahassee, Florida
    Current affiliation:
    1. Marie Z. Markarian, Intel Corporation, Hillsboro, Oregon
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  • Joseph B. Schlenoff

    Corresponding author
    • Department of Chemistry and Biochemistry, The Florida State University, Tallahassee, Florida
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Correspondence to: J. B. Schlenoff (E-mail: schlen@chem.fsu.edu)

ABSTRACT

Sulfonation of narrow polydispersity polystyrene, PS, standards remains the method of choice for generating polystyrene sulfonate, PSS, samples with defined composition. Although a variety of sulfonation techniques have been described, relatively little is reported on the material obtained, which is used for so many studies on the fundamental behavior of polyelectrolytes. Here, we show that powdered polystyrene treated with concentrated sulfuric acid (96%) at 90 °C without catalyst yields fully sulfonated PSS. Extensive characterization with 1H and 13C NMR as well as size exclusion chromatography coupled with static and dynamic light scattering shows no evidence of sulfone crosslinking or chain degradation under the conditions used. Though mono-sulfonated as soon as it dissolves in the acid, the PSS contains about 6% meta substitution. Sulfonation kinetics for this heterogeneous reaction depend strongly on particle size, sulfuric acid content and temperature. For preparing perdeuterated PSS from the corresponding PS it is essential to employ D2SO4, as about half of the aromatic units undergo H/D exchange during sulfonation. The remaining ortho H/D may be exchanged with extended exposure to the concentrated sulfuric acid, but the meta site is deactivated. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2416–2624

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