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Issue 48, 2017
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Novel imidazolium-based poly(ionic liquid)s with different counterions for self-healing

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Novel imidazolium-based norbornene polymerized ionic liquids (PILs) with different counterions (CH3SO3, CF3SO3, CF3(CF2)3SO3, FSI, Tf2N) for self-healing are synthesized via ring-opening metathesis polymerization (ROMP) utilizing the Grubbs third generation catalyst (G3). As proved by the changes in the chemical shift of the imidazolium proton in 1H NMR spectra in CDCl3, variation of the counterion brings different interaction intensities between imidazolium and counterions. The glass transition temperature (Tg) was mainly influenced by the size of the counterion. For large counterions such as FSI and Tf2N, they not only formed loose ionic aggregates leading to weak physical cross-links, but also acted as plasticizers in the polymer matrix, resulting in a decrease of Tg. X-ray scattering tests also proved that small counterions were prone to forming packed ion clusters leading to intensive ion aggregation. The ionic associations in the polymer matrix serve as physical cross-links, restricting the mobility of the surrounding polymer chain and improving the mechanical strength. However, sufficient chain mobility was in favor of the dynamic rearrangement of ion aggregation over the fracture surface that imparted the self-healing behavior. To balance the mechanical properties and healing performance, PIL blends with appropriate Tg were prepared by blending a high Tg PIL (such as CH3SO3, CF3SO3 or CF3(CF2)3SO3) with varying amounts of a low Tg PIL (i.e. Tf2N). Via this approach, the Tg of the resulting blends could be systemically tuned by adjusting the blending ratio and counterion. As expected, both excellent mechanical performance and self-healing capability of the well-designed PILs were achieved simultaneously.

Graphical abstract: Novel imidazolium-based poly(ionic liquid)s with different counterions for self-healing

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The article was received on 02 Aug 2017, accepted on 09 Oct 2017 and first published on 09 Oct 2017

Article type: Paper
DOI: 10.1039/C7TA06793C
Citation: J. Mater. Chem. A, 2017,5, 25220-25229
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    Novel imidazolium-based poly(ionic liquid)s with different counterions for self-healing

    J. Cui, F. Nie, J. Yang, L. Pan, Z. Ma and Y. Li, J. Mater. Chem. A, 2017, 5, 25220
    DOI: 10.1039/C7TA06793C

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