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SANS Investigation and Conductivity of Pure and Salt-Containing Poly(bismethoxyphosphazene)
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    SANS Investigation and Conductivity of Pure and Salt-Containing Poly(bismethoxyphosphazene)
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    Institut für Anorganische und Analytische Chemie, SFB 458, and International Graduate School of Chemistry (GSC-MS), Universität Münster, 48149 Münster, Germany, and Institut für Festkörperforschung, Forschungszentrum Jülich, 52425 Jülich, Germany
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    Macromolecules

    Cite this: Macromolecules 2008, 41, 6, 2212–2218
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    https://doi.org/10.1021/ma071429e
    Published February 28, 2008
    Copyright © 2008 American Chemical Society

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    Poly(bismethoxyphosphazene) (PBMP) was synthesized, giving polymer melts with Tg = −70.9 °C. The chain dynamics of melts and DMF solutions of poly(bismethoxyphosphazene) (PBMP) was investigated by Small-Angle Neutron Scattering (SANS). The radius of gyration Rg was found as 144.7 ± 0.2 Å, and the average MW from SANS was 95000 Da. DMF revealed to be a good solvent for this polymer. From the scattering intensity of polymer solutions for high q-data, the slope was −1.647 in almost exact agreement with the expected excluded volume exponent by Flory which is 5/3 affirming the good solvent property of DMF. GPC measurements of THF solutions were evaluated based on a universal calibration of polystyrene standards resulting in a rather similar value of 1.05 × 105 Da. Another series of SANS experiments was done with solutions of LiSO3CF3 (LiTf) in the title polymer. They also showed low Tg values down to −50 °C at 15 wt %. The SANS results (5 and 10 mol % LiTf as referred to the monomer units) showed almost no effect of the dissolved salt on the melt conformation of the polyphosphazene (almost random coil), and thus revealed a rather small interaction between salt and polymer. We also measured the ionic conductivity of salt-in-polymer systems with concentrations from 5 to 20 wt % LiTf. The room-temperature conductivity was 1.7 × 10-5 S/cm at 20 wt % LiTf and is thus rather high. The low interaction between salt and polymeric solvent is in agreement with the predominance of neutral ion pairs which is often observed in such polymer electrolytes.

    Copyright © 2008 American Chemical Society

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     Institut für Anorganische und Analytische Chemie, and SFB 458, Universität Münster.

    §

     International Graduate School of Chemistry (GSC-MS).

     Institut für Festkörperforschung, Forschungszentrum Jülich.

    *

     Corresponding author. E-mail [email protected]. Telephone:  +49 251 83 33115. Fax:  +49 251 83 33193.

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    This article is cited by 7 publications.

    1. Barbara Koch, Michael Vogel. Dynamics of a Polyphosphazene Melt Studied by Solid-State 2H NMR. Macromolecules 2009, 42 (2) , 531-536. https://doi.org/10.1021/ma802421e
    2. K. Shivaji Sharma, Grégory Durand, Fabrice Giusti, Blandine Olivier, Anne-Sylvie Fabiano, Paola Bazzacco, Tassadite Dahmane, Christine Ebel, Jean-Luc Popot and Bernard Pucci . Glucose-Based Amphiphilic Telomers Designed to Keep Membrane Proteins Soluble in Aqueous Solutions: Synthesis and Physicochemical Characterization. Langmuir 2008, 24 (23) , 13581-13590. https://doi.org/10.1021/la8023056
    3. Zhengping Zhao, Zhao Xu, Jiayi Chen, Mingqiang Zhong, Jiahao Wang, Jia Wei Chew. A review on functional applications of polyphosphazenes as multipurpose material for lithium-ion batteries. Journal of Energy Storage 2024, 85 , 111049. https://doi.org/10.1016/j.est.2024.111049
    4. Klaus Funke. Solid State Ionics: from Michael Faraday to green energy—the European dimension. Science and Technology of Advanced Materials 2013, 14 (4) , 043502. https://doi.org/10.1088/1468-6996/14/4/043502
    5. Marina Burjanadze, Yunus Karatas, Nitin Kaskhedikar, Lutz M. Kogel, Sebastian Kloss, Ann-Christin Gentschev, Martin M. Hiller, Romek A. Müller, Raphael Stolina, Preeya Vettikuzha, Hans-Dieter Wiemhöfer. Salt-in-Polymer Electrolytes for Lithium Ion Batteries Based on Organo-Functionalized Polyphosphazenes and Polysiloxanes. Zeitschrift für Physikalische Chemie 2010, 224 (10-12) , 1439-1473. https://doi.org/10.1524/zpch.2010.0046
    6. Frederick F. Stewart. Phosphazenes. 2010, 308-352. https://doi.org/10.1039/9781849730839-00308
    7. Derek P. Gates. Inorganic and organometallic polymers. Annual Reports Section "A" (Inorganic Chemistry) 2009, 105 , 397. https://doi.org/10.1039/b818284c

    Macromolecules

    Cite this: Macromolecules 2008, 41, 6, 2212–2218
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ma071429e
    Published February 28, 2008
    Copyright © 2008 American Chemical Society

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