Comb-Shaped Supramolecules of Emeraldine Base Form of Polyaniline Due to Coordination with Zinc Dodecyl Benzenesulfonate and Their Plasticized Self-Organized Structures

Abstract

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.

Nanocomposites of silver nanoparticle and dinonylnaphthalene disulfonic acid‐doped thermoreversible polyaniline gel

“…From the UV-vis spectra (Fig. 7), it is apparent that PANI (EB) has peaks at 324 nm corresponding to p-p* transition of benzonoid ring and a broad band at 635 nm due to the electronic excitation from benzonoid ring to quinonoid ring [49][50][51][52]. In the PANI-DNNDSA gel and in the GMNCs, the 635 nm peak is absent and a new peak at $840 nm appears, indicating doping is complete in all the PANI-DNNDSA systems.…”

Studies on the synthesis of low molecular weight, one‐dimensional polyanilines prepared by fast emulsion polymerization using (n‐dodecylbenzenesulfonic acid)/HCl emulsifiers

“…), where only λ max around 780 nm can be seen, corresponding to the presence of a poorly conjugated, coiled polyaniline chain. These nanotubular or nanofibrous molecules are similar to hairy rod molecules which have a tendency to arrange into an ordered, layered structure, and give a well‐defined layered structure after orientation, as illustrated in the WAXD patterns and AFM micrographs.…”

Polyaniline-graphene composites with a three-dimensional array-based nanostructure for high-performance supercapacitors

“…The significant increase in wavelength of AFG suggests that the electronic conjugation within the carbon framework of graphene has been restored after chemical reduction and conjugation is further extended to those grafted p-phenylenediamine through covalent bonds. After polymerization, the PAFG composite showed three new peaks at 353, 442, and 853 nm corresponding to p-p * , p * band to polaron band and p band to polaron band transitions of PANI, respectively [19,20], which is a typical characteristic of the conducting emeraldine state of PANI. Compared with PANI, the absorption peak of PAFG was redshifted to 853 from 819 nm.…”