We show that the emeraldine base form of polyaniline (PANI) forms self-organized (mesomorphic) structures upon mixing with an amphiphilic oligomer zinc dodecyl benzenesulfonate, Zn(DBS)2. The number of Zn(DBS)2 molecules vs the number of PhN repeat units of PANI was selected to be x = 0, 0.125, 0.25, 0.5, and 1.0, and the mixtures were denoted as PANI[Zn(DBS)2] x according to their nominal compositions. PANI consists of alternating quinone diimine and benzene diamine groups. FT-IR and UV−vis spectroscopies reveal changes in the quinone diimine moieties upon adding Zn(DBS)2, thus suggesting coordination to the iminic nitrogens to form comb-shaped supramolecules PANI[Zn(DBS)2]0.5. Their structure formation was studied using small-angle X-ray scattering and electron microscopy. The competition between the attraction (coordination) and repulsion (dodecyl tails) leads to a self-organized lamellar phase with a long period of ca. 31 Å. Further increase of Zn(DBS)2 did not reveal clear changes in FT-IR and UV−vis but results in plasticization to render viscous fluid upon heating for x = 1.0, in contrast to the uncomplexed PANI which is infusible.

Mesomorphic structure of poly(styrene)-block-poly(4-vinylpyridine) with oligo(ethylene oxide)sulfonic acid side chains as a model for molecularly reinforced polymer electrolyte Citation for published version (APA): Kosonen, H., Valkama, S., Hartikainen, J., Eerikainen, H., Torkkeli, M., Jokela, K., ... Eerikäinen, H. (2002). Mesomorphic structure of poly(styrene)-block-poly(4-vinylpyridine) with oligo(ethylene oxide)sulfonic acid side chains as a model for molecularly reinforced polymer electrolyte. Macromolecules, 35(27), ABSTRACT: We report self-organized polymer electrolytes based on poly(styrene)-block-poly(4-vinylpyridine) (PS-block-P4VP). Liquidlike ethylene oxide (EO) oligomers with sulfonic acid end groups are bonded to the P4VP block, leading to comb-shaped supramolecules with the PS-block-P4VP backbone. Lithium perchlorate (LiClO 4) has been added to the EO-rich domains. Small-and wide-angle X-ray scattering in combination with Fourier transformation infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), ac impedance, and dynamic mechanical spectroscopy (DMA) suggests alternating lamellae of reinforcing glassy PS domains and ionically conducting "nanochannels" consisting of poly(4-vinylpyridinium), oligomeric ethylene oxide sulfonates, and LiClO 4. The long period of the self-organization is ca. 300 Å. So far, the ionic conductivity levels remained relatively low, i.e., 10 -7 -10 -6 S/cm at room temperature and 10 -5 -10 -4 S/cm at 80°C. However, as self-organization of polymeric supramolecules allows combining glassy reinforcing domains and well-plasticized domains consisting of oligomers with high segmental motions, there may exist possibilities to tune feasible combination of electrical and mechanical properties.

No abstract

No abstract