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Conducting materials prepared by the oxidation of p-phenylenediamine with p-benzoquinone

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Abstract

p-Phenylenediamine was oxidized with p-benzoquinone in the aqueous solutions of methanesulfonic acid (MSA). The conductivity of the products increased with increasing concentration of MSA from 1.5 × 10−12 S cm−1 in 0.1 M MSA up to 3.4 × 10−4 S cm−1 in 5 M MSA. The low-molecular-weight products are basically composed of one p-benzoquinone and two p-phenylenediamine molecules. Their molecular structure is discussed on the basis of mass, Fourier-transform infrared, Raman, NMR and electron paramagnetic resonance (EPR) spectroscopies. The formation of 2,5-di(p-phenylenediamine)-p-benzoquinone protonated with methanesulfonic acid best complies with the information provided by spectroscopic techniques. Its conversion to hydroquinone tautomer explains the formation of unpaired spins observed by EPR and their potential contribution to the conduction.

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References

  1. Ćirić-Marjanović G (2013) Recent advances in polyaniline research: Polymerization mechanisms, structural aspects, properties and applications. Synth Met 177:1–47

    Article  Google Scholar 

  2. Stejskal J, Sapurina I, Trchová M (2010) Polyaniline nanostructures and the role of aniline oligomers in their formation. Prog Polym Sci 35:1420–1481

    Article  CAS  Google Scholar 

  3. Stejskal J, Trchová M (2012) Aniline oligomers versus polyaniline. Polym Int 61:240–251

    Article  CAS  Google Scholar 

  4. Stejskal J, Bober P, Trchová M, Horský J, Pilař J, Walterová Z (2014) The oxidation of aniline with p-benzoquinone and its impact on the preparation of a conducting polymer, polyaniline. Synth Met 192:66–73

    Article  CAS  Google Scholar 

  5. Mather BD, Viswanathan K, Miller KM, Long TE (2006) Michael addition reactions in macromolecular design for emerging technologies. Prog Polym Sci 31:487–531

    Article  CAS  Google Scholar 

  6. Phani KLN, Pitchumani S, Muralidharan S, Ravichandran S, Iyer SVK (1993) Electrosynthesis of polyamino-benzoquinone (PAQ) polymers. J Electroanal Chem 353:315–322

    Article  CAS  Google Scholar 

  7. Muralidharan S, Phani KLN, Pitchumani S, Ravichandran S, Iyer SVK (1995) Polyamino-benzoquinone polymers: a new class of corrosion inhibitors for mild steel. J Electrochem Soc 142:1478–1483

    Article  CAS  Google Scholar 

  8. Vaccaro E, Simone CD, Scola DA (2000) Amino-p-benzoquinone adducts and polymers as adhesion promoters for steel. J Adhes 72:157–176

    Article  CAS  Google Scholar 

  9. Grgur BN (2014) On the role of aniline oligomers on the corrosion protection of mild steel. Synth Met 187:57–60

    Article  CAS  Google Scholar 

  10. Vaccaro E, Scola DA (1999) New applications of polyaminoquinones. Chemtech 29:15–23

    CAS  Google Scholar 

  11. Mrlik M, Sedlacik M, Pavlinek V, Bober P, Trchová M, Stejskal J, Saha P (2013) Electrorheology of aniline oligomers. Colloid Polym Sci 291:2079–2086

    Article  CAS  Google Scholar 

  12. Mrlik M, Pavlinek V, Alajdalawi S, Saha P, Bober P, Stejskal J (2013) Electrorheology of aniline-oligomer suspensions under oscillatory shear. J Phys Conf Ser 412:012007 (1–6)

    Article  Google Scholar 

  13. Vonlanthen D, Lazarev P, See KA, Wudl F, Heeger AJ (2014) A stable polyaniline-benzoquinone-hydroquinone supercapacitor. Adv Mater 26:5095–5100

    Article  CAS  Google Scholar 

  14. Dennany L, Innis PC, McGovern ST, Wallace GG, Forster RJ (2014) Electronic interactions within composites of polyanilines formed under acidic and alkaline conditions. Conductivity, ESR, Raman, UV-vis and fluorescence studies. Phys Chem Chem Phys 13:3303–3310

    Article  Google Scholar 

  15. Mrlik M, Moucka R, Ilčíková M, Bober P, Kazantseva N, Špitálský Z, Trchová M, Stejskal J (2014) Electrical transport in aniline-based oligomers. Synth Met 192:37–42

    Article  CAS  Google Scholar 

  16. Durgaryan AA, Arakelyan RA, Durgaryan NA (2014) Oxidative polymerization of p-phenylenediamine. Russ J Gen Chem 84:1095–1100

    Article  CAS  Google Scholar 

  17. Hall HK Jr, Padias AB, Boone HW (2007) Condensation routes to polyaniline and its analogs. J Polym Sci A Polym Chem 45:4751–4763

    Article  CAS  Google Scholar 

  18. Evaerts A, Roberts S, Hall HK Jr (1986) Synthesis and properties of semiconducting aromatic polyquinonediimines. J Polym Sci A Polym Chem 24:1703–1716

    Article  Google Scholar 

  19. Kour H, Paul S, Singh PP, Gupta R (2014) A mild and simple method for the synthesis of substituted phenazines. Synlett 25:495–500

    CAS  Google Scholar 

  20. Stejskal J (2015) Polymers of phenylenediamines. Prog Polym Sci 41:1–31

    Article  CAS  Google Scholar 

  21. Bober P, Stejskal J, Trchová M, Prokeš J (2011) Polyaniline–silver composites prepared by the oxidation of aniline with mixed oxidants, silver nitrate and ammonium peroxydisulfate: the control of silver content. Polymer 52:5947–5952

    Article  CAS  Google Scholar 

  22. Stejskal J (2013) Conducting polymer–silver composites. Chem Pap 67:814–848

    Article  CAS  Google Scholar 

  23. Ćirić-Marjanović G, Marjanović B, Bober P, Rozlívková Z, Stejskal J, Trchová M, Prokeš J (2011) The oxidative polymerization of p-phenylenediamine with silver nitrate: Toward highly conducting micro/nanostructured silver/conjugated polymer composites. J Polym Sci Polym Chem 49:3387–3403

    Article  Google Scholar 

  24. Silva CHB, Ferreira DC, Ando RA, Temperini MLA (2012) Aniline-1,4-benzoquinone as a model system for the characterization of products from aniline oligomerization in low acidic media. Chem Phys Lett 551:130–133

    Article  CAS  Google Scholar 

  25. Ferreira DC, Pires JR, Temperini MLA (2011) Spectroscopic characterization of oligoaniline microspheres obtained by an aniline–persulfate approach. J Phys Chem B 115:1368–1375

    Article  CAS  Google Scholar 

  26. Plachy T, Sedlacik M, Pavlinek V, Morávková Z, Hajná M, Stejskal J (2013) An effect of carbonization on the electrorheology of poly(p-phenylenediamine). Carbon 63:187–195

    Article  CAS  Google Scholar 

  27. Mizoguchi K, Nechtschein M, Travers JP (1991) Spin dynamics and conductivity in polyaniline: temperature dependence. Synth Met 41–43:113–116

    Article  Google Scholar 

  28. Sariciftci NS, Heeger AJ, Cao Y (1994) Paramagnetic susceptibility of highly conducting polyaniline: Disordered metal with weak electron-electron interactions (Fermi glass). Phys Rev B 49:5988–5992

    Article  CAS  Google Scholar 

  29. Dyakonov V, Frankevich E (1998) On the role played by polaron pairs in photophysical processes in semiconducting polymers. Chem Phys 227:203–217

    Article  CAS  Google Scholar 

  30. Weil JA, Bolton JR (2008) Electron paramagnetic resonance. Elementary theory and practical applications, 2nd edn. Wiley-Interscience, New York

    Google Scholar 

  31. Lotina-Hennsen B, Achnine L, Ruvalcaba NM, Ortiz A, Hernandez J, Farfan N, Aguilar-Martınez M (1998) 2,5-Diamino-p-benzoquinone derivatives as photosystem I electron acceptors: synthesis and electrochemical and physicochemical properties. J Agric Food Chem 46:724–730

    Article  CAS  Google Scholar 

  32. Joseph-Nathan P, Abramo-Bruno D, Ortega DA (1981) Carbon NMR studies of benzoquinones. Org Magn Reson 15:311–316

    Article  CAS  Google Scholar 

  33. Scheffer JR, Wong YF, Patil AO, Curtin DY, Paul IC (1985) CPMAS 13CNMR spectra of quinones, hydroquinones, and their complexes. Use of CMR to follow a reaction in the solid state. J Am Chem Soc 107:4898–4904

    Article  CAS  Google Scholar 

  34. Kolbert AC, Caldarelli S, Their KF, Sariciftci NS, Cao Y, Heeger AJ (1995) NMR evidence for the metallic nature of highly conducting polyaniline. Phys Rev B 51:1541–1545

    Article  CAS  Google Scholar 

  35. Reepmester J (1980) Application of solid state 13C NMR to the study of polymorphs, clathrates and complexes. Chem Phys Lett 74:536–538

    Article  Google Scholar 

  36. López C, Claramunt RM, Elguero J (2008) Oxalic acid/phenols and oxalic acid/cholesterol co-crystals: a solid state 13C CPMAS NMR study ARKIVOC (iv): 33–46

  37. Kříž J, Starovoytova L, Trchová M, Konyushenko EN, Stejskal J (2009) NMR investigation of aniline oligomers produced in the early stages of oxidative polymerization of aniline. J Phys Chem B 113:6666–6673

    Google Scholar 

  38. Zujovic ZD, Bowmaker GA, Nieuwoudt M, Kilmartin PA (2013) Nanostructures obtained in the oxidative polymerization of aniline: effects of polarons. Polymer 54:6363–6372

    Article  CAS  Google Scholar 

  39. Panda M, Srivinas V, Thakur AK (2014) Universal microstructure and conductivity relaxation of polymer-conductor composites across the percolation threshold. Curr Appl Phys 14:1596–1606

    Article  Google Scholar 

Download references

Acknowledgments

The authors thank the Czech Science Foundation (P205/12/0911) and the Czech–Austrian mobility project (7AMB14AT005) for financial support. LDI mass spectra has kindly been provided by Z. Walterová from IMC in Prague.

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Authors and Affiliations

  1. Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06, Prague 6, Czech Republic

    Jaroslav Stejskal, Miroslava Trchová, Zuzana Morávková, Patrycja Bober, Michal Bláha, Jiří Pfleger & Przemysław Magdziarz

  2. Faculty of Mathematics and Physics, Charles University in Prague, 182 00, Prague 8, Czech Republic

    Jan Prokeš

  3. Linz Institute for Organic Solar Cells/Institute of Physical Chemistry, Johannes Kepler University of Linz, 4040, Linz, Austria

    Marek Havlicek & Niyazi Serdar Sariciftci

  4. University of Würzburg and Bavarian Centre for Applied Energy Research (ZAE Bayern), 97074, Würzburg, Germany

    Andreas Sperlich & Vladimir Dyakonov

  5. Polymer Electronics Research Centre and NMR Centre, School of Chemical Sciences, The University of Auckland, Auckland, 1142, New Zealand

    Zoran Zujovic

Authors
  1. Jaroslav Stejskal
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  2. Miroslava Trchová
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  12. Vladimir Dyakonov
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Correspondence to Jaroslav Stejskal.

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Stejskal, J., Trchová, M., Morávková, Z. et al. Conducting materials prepared by the oxidation of p-phenylenediamine with p-benzoquinone. J Solid State Electrochem 19, 2653–2664 (2015). https://doi.org/10.1007/s10008-015-2838-3

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  • DOI: https://doi.org/10.1007/s10008-015-2838-3

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