Characterization and DFT calculation of poly(m-anisidine) synthesized with different dopant acids

Veras, Tiago Neves; Carolino, Adriano de Souza; Lima, Suzan Xavier; Biondo, Matheus Moraes; Santos, Nataly A.; Campelo, Pedro Henrique; Leyet, Y.; Frota, H.O.; Sanches, Edgar Aparecido

doi:10.1016/j.molstruc.2019.127182

Cited by 7 publications

(10 citation statements)

References 51 publications

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“…Several parameters influence on the mobility of counter ions along the polymer chains in ICP materials. These factors are mainly related to the (i) synthesis methodology [32][33][34], (ii) regular packing of the polymer chains (or polymer crystallinity), (iii) ring side group at the ortho, meta, or para positions [8,[35][36][37], and (iv) the nature of the doping acid and counter ion size [38], as well as (v) the possible chemical and/or physical interactions between counter ions and ring side groups [39].…”

Section: Electrical Conductivitymentioning

confidence: 99%

Poly(o-methoxyaniline) Chain Degradation Based on a Heat Treatment (HT) Process: Combined Experimental and Theoretical Evaluation

et al. 2022

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Poly(o-methoxyaniline) emeraldine-salt form (ES-POMA) was chemically synthesized using hydrochloric acid and subjected to a heat treatment (HT) process for 1 h at 100 °C (TT100) and 200 °C (TT200). The HT process promoted a progressive decrease in crystallinity. The Le Bail method revealed a decomposition from tetrameric to trimeric-folded chains after the HT process. The unheated POMA-ES presented a globular vesicular morphology with varied micrometric sizes. The heat treatment promoted a reduction in these globular structures, increasing the non-crystalline phase. The boundary length (S) and connectivity/Euler feature (χ) parameters were calculated from the SEM images, revealing that ES-POMA presented a wide distribution of heights. The TT100 and TT200 presented a narrow boundary distribution, suggesting smoother surfaces with smaller height variations. The UV-VIS analysis revealed that the transition at 343 nm (nonlocal π → π*) was more intense in the TT200 due to the electronic delocalization, which resulted from the reduced polymer chain caused by the HT process. In addition to the loss of conjugation, counter ion withdrawal reduced the ion-chain interaction, decreasing the local electron density. This result shows the influence of the chlorine counter ions on the peaks position related to the HOMO → LUMO transition, since the π → polaron transition occurs due to the creation of the energy states due to the presence of counter ions. Finally, the electrical conductivity decreased after the HT process from 1.4 × 10−4 S.cm−1 to 2.4 × 10−6 S.cm−1 as result of the polymer deprotonation/degradation. Thus, this paper proposed a systematic evaluation of the POMA molecular structure and crystallite size and shape after heat treatment.

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Section: Electrical Conductivitymentioning

confidence: 99%

Poly(o-methoxyaniline) Chain Degradation Based on a Heat Treatment (HT) Process: Combined Experimental and Theoretical Evaluation

et al. 2022

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“…The polyconjugated structures of intrinsically conducting polymers (ICPs) play an important role, mainly in their crystal structures and electrical properties [ 1 , 2 , 3 ]. Some advantages of conjugated polymers are based on their methods of synthesis [ 4 ] and good environmental stability, allowing for the development of novel materials [ 5 , 6 , 7 ].…”

Section: Introductionmentioning

confidence: 99%

“…Structural aspects in polyanilines continue to be an interesting research topic [ 8 , 9 , 10 ]. Efforts have been devoted to improving their crystallinity, processability, and electrical conductivity by using appropriate functionalized protonic acids, novel mechanisms of polymerization, and substituted polyanilines [ 2 , 4 , 11 ]. Polyaniline derivatives are based on a suitable substituent attached either at the nitrogen atom or in the phenyl ring of the repeated unit [ 2 , 12 , 13 , 14 ].…”

Section: Introductionmentioning

confidence: 99%

“…Among the substituted polyaniline derivatives, poly( p -anisidine) (PPA) is a polyaniline presenting a methoxy (–OCH 3 ) group at the para position of the phenyl ring [ 16 , 17 , 18 ]. The electron-donating substituent groups in the aromatic rings strongly introduce the conformational modifications of conjugated polymers [ 2 ] influencing a range of physicochemical properties. Structural, morphological, thermal, and electrical properties of ortho - and meta -substituted polyanilines have been widely reported [ 2 , 4 , 11 ].…”

Section: Introductionmentioning

confidence: 99%

“…The electron-donating substituent groups in the aromatic rings strongly introduce the conformational modifications of conjugated polymers [ 2 ] influencing a range of physicochemical properties. Structural, morphological, thermal, and electrical properties of ortho - and meta -substituted polyanilines have been widely reported [ 2 , 4 , 11 ]. However, systematic reports on poly( p -anisidine) (PPA) were not found in the scientific literature.…”

Section: Introductionmentioning

confidence: 99%

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Head-to-Tail and Head-to-Head Molecular Chains of Poly(p-Anisidine): Combined Experimental and Theoretical Evaluation

et al. 2022

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Poly(p-anisidine) (PPA) is a polyaniline derivative presenting a methoxy (–OCH3) group at the para position of the phenyl ring. Considering the important role of conjugated polymers in novel technological applications, a systematic, combined experimental and theoretical investigation was performed to obtain more insight into the crystallization process of PPA. Conventional oxidative polymerization of p-anisidine monomer was based on a central composite rotational design (CCRD). The effects of the concentration of the monomer, ammonium persulfate (APS), and HCl on the percentage of crystallinity were considered. Several experimental techniques such as X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), multifractal analysis, Nuclear Magnetic Resonance (13C NMR), Fourier-transform Infrared spectroscopy (FTIR), and complex impedance spectroscopy analysis, in addition to Density Functional Theory (DFT), were employed to perform a systematic investigation of PPA. The experimental treatments resulted in different crystal structures with a percentage of crystallinity ranging from (29.2 ± 0.6)% (PPA1HT) to (55.1 ± 0.2)% (PPA16HT-HH). A broad halo in the PPA16HT-HH pattern from 2θ = 10.0–30.0° suggested a reduced crystallinity. Needle and globular-particle morphologies were observed in both samples; the needle morphology might have been related to the crystalline contribution. A multifractal analysis showed that the PPA surface became more complex when the crystallinity was reduced. The proposed molecular structures of PPA were supported by the high-resolution 13C NMR results, allowing us to access the percentage of head-to-tail (HT) and head-to-head (HH) molecular structures. When comparing the calculated and experimental FTIR spectra, the most pronounced changes were observed in ν(C–H), ν(N–H), ν(C–O), and ν(C–N–C) due to the influence of counterions on the polymer backbone as well as the different mechanisms of polymerization. Finally, a significant difference in the electrical conductivity was observed in the range of 1.00 × 10−9 S.cm−1 and 3.90 × 10−14 S.cm−1, respectively, for PPA1HT and PPA16HT-HH.

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Synthesis and investigation of methyl and methoxy groups containing polyaniline derivatives in organic medium

Miraqyan,

Durgaryan,

Durgaryan

2024

Polym. Bull.

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Characterization and DFT calculation of poly(m-anisidine) synthesized with different dopant acids

Cited by 7 publications

References 51 publications

Poly(o-methoxyaniline) Chain Degradation Based on a Heat Treatment (HT) Process: Combined Experimental and Theoretical Evaluation

Poly(o-methoxyaniline) Chain Degradation Based on a Heat Treatment (HT) Process: Combined Experimental and Theoretical Evaluation

Head-to-Tail and Head-to-Head Molecular Chains of Poly(p-Anisidine): Combined Experimental and Theoretical Evaluation

Synthesis and investigation of methyl and methoxy groups containing polyaniline derivatives in organic medium

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