A series of novel polymerized ionic liquids (PILs) contained imidazolium, poly (2,5‐bis{[6‐(1‐butyl‐3′‐imidazolium)hexyl] oxy carbonyl}styrene salts) (denoted as P1X−, X−Br−, BF4−, PF6− and TFSI−) were successfully synthesized via radical polymerization. The chemical structures of the monomers and their corresponding PILs were confirmed by 1H NMR, 13C NMR, and Fourier transform infrared spectroscopy. Thermogravimetric analysis results showed that these PILs had excellent thermal stability. The phase transitions and liquid‐crystalline (LC) behaviors of these polymers were investigated by differential scanning calorimetry, polarized light microscopy (PLM), and wide‐angle X‐ray diffraction. The combined experimental results showed that all the PILs could form hexagonal columnar (ϕH) LC ordered structures because of the strong interaction between the anions and cations in the side groups except for P1TFSI−. The conductivities of monomers and PILs were sketchily investigated, and monomers had higher conductivities than those of conprespoding PILs. For comparison, we have synthesized a polymer without counter‐anion, but similar to the chemical structure of P1X−, poly (2, 5‐bis{[6‐(4‐butoxy‐4′‐oxy phenyl) hexyl] oxycarbonyl} styrene) (denoted as P2). In this case, phenyl took place of imidazolium of side chain, and LC ordered structure did not form. The comparison between P1X− and P2 suggested that ion played an important role in the constructing of LC ordered structure. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

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Ionic liquid crystalline polymers (ILCPs) are a class of macromolecular architectures with mesogenic groups and ionic species and they have attracted great interest in the fields of polymer chemistry and materials science lately [1][2][3]. The combination of electrostatic interaction with liquid crystalline (LC) ordering yields ILCPs with excellent mechanical properties, rheological processability, piezoelectric performance, and optical variable performance [1][2][3][4][5][6][7]. Generally, ionic interaction promotes the ILCPs to form ionic clusters resulting in a reversible physical gelation [1,8,9]. Moreover, incorporation of the ions and selection of the type of ion chemistry can effectively improve the miscibility with other polymers. Therefore, ILCPs are versatile candidates to construct new high-performance functional mate- 536Combined main-chain/side-chain ionic liquid crystalline polymer based on 'jacketing' effect: Design, synthesis, supra-molecular self-assembly and photophysical properties Abstract. Reasonably fabricating ordered structures of ionic polymers is very important for the development of novel functional materials. By combining the ions and liquid cry stalline polymer, we successfully designed and synthesized a series of novel combined main-chain/side-chain ionic liquid crystalline polymer (MCSC-ILCPs) containing imidazolium groups and different counter-anions, poly (2,5-bis{[6-(4-butoxy-4!-imidazolium biphenyl)hexyl]oxycarbonyl}styrene salts) poly(BImBHCS-X) with the following types of counter-anions (Br", BF 4 ", PF 6 " and TFSI"). Combined technologies confirmed the chemical structures of the monomers and polymers with imidazolium cation and different counter-anions. Differential scanning calorimetry (DSC), polarized light microscopy (PLM) and one-and two-dimensional wide-angle X-ray diffraction (1D and 2D WAXD) results illustrated that the LC structures and the transitions of ordered structures depended on the nature of the counter-anion employed. The polymers with Br" and BF 4 " counter-anions exhibited smectic A (SmA) LC behavior below the isotropic temperature. The another one, poly(BImBHCS-TFSI) with the large volume of the TFSI" anion destroyed the packing of the LC ordered structure resulting in an amorphous structure. The photophysical properties of the polymers prepared can be adjusted by tuning the ionic interaction of the polymers by switching the counter-anion.

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