Vol. 6 No. 1 (2022)
Historical Articles

The Early History of Polyaniline II: Elucidation of Structure and Redox States

Seth C. Rasmussen
Department of Chemistry and Biochemistry, North Dakota State University, Fargo, ND 58108 USA
Bio

Published 2022-03-07

Keywords

  • polyaniline,
  • aniline black,
  • emeraldine,
  • nigraniline,
  • structure elucidation

How to Cite

Rasmussen, S. C. (2022). The Early History of Polyaniline II: Elucidation of Structure and Redox States. Substantia, 6(1), 107–119. https://doi.org/10.36253/Substantia-1425

Abstract

Polyaniline, one of the primary parent conducting polymers, is a quite old material with a history dating back to 1834. With the distinction of being the oldest known fully synthetic polymer and successfully commercialized as several popular cotton dyes in the 1860s, this material was originally known by the name of its black dye, aniline black.  Of course, throughout this early history, the chemical identity and structure of these early polyaniline products were completely unknown, and it was not until the 1870s that initial attempts began to reveal various structural aspects. The current report will present a detailed historical account of the efforts to determine the structures of these early aniline oxidation products over the time period of ca. 1870-1915. In addition to the identity and structure of specific products, studies revealing the interconversion of one species to another via both redox and acid-based processes will also be discussed, with these collective efforts resulting in a comprehensive model of these materials that has remained essentially unchanged to this day.

References

  1. E. M. Geniès, A. Boyle, M. Lapkowski, C. Tsintavis, Polyaniline: A Historical Survey. Synth. Met. 1990, 36, 139-182.
  2. D. Li, J. Huang, R. B. Kaner, Polyaniline Nanofibers: A Unique Polymer Nanostructure for Versatile Applications. Acc. Chem. Res. 2009, 42, 135-145.
  3. Y. Wang, Preparation and application of polyaniline nanofibers: an overview. Polym. Intern. 2018, 67, 650-669.
  4. P. Zarrintaj, Z. Ahmadi, H. Vahabi, F. Ducos, M. Reza Saeb, M. Mozafari, Polyaniline in retrospect and prospect. Mater. Today: Proc. 2018, 5, 15852-15860.
  5. N. Kumari Jangid, S. Jadoun, N. Kaur, A review on high-throughput synthesis, deposition of thin films and properties of polyaniline. Euro. Polym. J. 2020, 125, 109485.
  6. J. Sebastian, J. M. Samuel, Recent advances in the applications of substituted polyanilines and their blends and composites. Polym. Bull. 2020, 77, 6641-6669.
  7. E. N. Zare, P. Makvandi, B. Ashtari, F. Rossi, A. Motahari, G. Perale, Progress in Conductive Polyaniline-Based Nanocomposites for Biomedical Applications: A Review. J. Med. Chem. 2020, 63, 1-22.
  8. Q. N. Al-Haidary, A. M. Al-Mokaram, F. M. Hussein, A. H. Ismail, Development of polyaniline for sensor applications: a review. J. Phys.: Conf. Ser. 2021, 1853, 012062.
  9. S. C. Rasmussen, Electrically Conducting Plastics: Revising the History of Conjugated Organic Polymers. In 100+ Years of Plastics. Leo Baekeland and Beyond (Eds.: E. T. Strom, S. C. Rasmussen), American Chemical Society: Washington, DC 2011, pp. 147-163.
  10. S. C. Rasmussen, Early History of Conductive Organic Polymers. In Conductive Polymers: Electrical Interactions in Cell Biology and Medicine (Eds.: Z. Zhang, M. Rouabhia, S. Moulton) CRC Press, Boca Raton, FL 2017, pp. 1-21.
  11. S. C. Rasmussen, Early history of Conjugated Polymers: From their Origins to the Handbook of Conducting Polymers. In Handbook of Conducting Polymers, 4th Ed (Eds.: J. R. Reynolds, T. A. Skotheim, B. Thompson), CRC Press: Boca Raton, FL 2019, pp. 1-35.
  12. S. C. Rasmussen, Conjugated and Conducting Organic Polymers: The First 150 Years. ChemPlusChem 2020, 85, 1412-1429.
  13. S. C. Rasmussen, The Early History of Polyaniline: Discovery and Origins. Substantia 2017, 1(2), 99-109.
  14. S. C. Rasmussen, Early History of Polyaniline—Revisited: Russian Contributions of Fritzsche and Zinin. Bull. Hist. Chem. 2019, 44, 123-133.
  15. F. F. Runge, Ueber einige Producte der Steinkohlendestillation. Ann. Phys. Chem. 1834, 31, 513-524.
  16. E. Simon, Ueber den flüssigen Storax (Styrax liquidas). Ann. Pharm. 1839, 31, 265-277.
  17. S. C. Rasmussen, Revisiting the Early History of Synthetic Polymers: Critiques and New Insights. Ambix 2018, 65, 356–372.
  18. P. Constantini, G. Belorgey, M. Jozefowicz, R. Buvet, Préparation, propriétés acides et formation de complexes anioniques de polyanilines oligomères. C. R. Seances Acad. Sci. 1964, 258, 6421-6424.
  19. M. Jozefowicz, G. Belorgey, L.-T. Yu, R. Buvet, Oxydation et réduction de polyanilines oligomères. C. R. Seances Acad. Sci. 1965, 260, 6367-6370.
  20. M.-F. Combarel, G. Belorgey, M. Jozefowicz, L.-T. Yu, R. Buvet, Conductivité en courant continu des polyanilines oligomers: Influence de l'état acide-base sur Ia conductivité électronique. C. R. Seances Acad. Sci. 1966, 262, 459-6370.
  21. H. Rheineck, Ein Beitrag zur Kenntniss der Natur des Anilinschwarz. Dinglers Polytech. J. 1872, 203, 485-489.
  22. Verzeichnis der Beamten, Lehrer und Studirenden der königlich württembergi?chen Universität Tübingen in dem Sommerhalbjahr 1863. Tübingen, p. 27.
  23. H. Rheineck, Ueber das Verhalten des Allantoïns zu Natrium. Ann. Chem. Pharm. 1865, 134, 219-228.
  24. H. Rheineck, Ein Colorimeter. Dinglers Polytech. J. 1871, 201, 433-435.
  25. H. Rheineck, Ueber die Gührungserscheinungen. Dinglers Polytech. J. 1871, 202, 282-287.
  26. H. Rheineck, Ueber eine maaßanalytische Be?timmung des Eisens und Ferrocyans. Dinglers Polytech. J. 1871, 202, 154-159.
  27. H. Rheineck, Ein Beitrag zur Kenntniß der Natur des Anilinschwarz. Polytech. Centralblatt 1872, 38, 667-670.
  28. H. Rheineck, Beitrag zur Kenntniss der Natur des Anilinschwarz. Chemisches Centralblatt 1872, 43, 295-296.
  29. H. Rheineck, berichtet über Versuche, die er betreffs der Bildung von Anilinschwarz auf dem Gewebe angestellt hat. Jahresbericht Leistungen. Chem. Tech. 1873, 18, 710-711.
  30. R. Nietzki, Ueber Anilinschwarz. Ber. Dtsch. Chem. Ges. 1876, 9, 616-620.
  31. R. Nietzki, Ueber Anilinschwarz. Ber. Dtsch. Chem. Ges. 1876, 9, 1168-1170.
  32. H.-D. Schwarz, Nietzki, Rudolf Hugo. Neue Deutsche Biographie 1999, 19, 248.
  33. M. Kurz, Nietzki, Rudolf. Historisches Lexikon der Schweiz (HLS), Version 03.06.2010. https://hls-dhs-dss.ch/de/articles/045058/2010-06-03/ (accessed 09, 2021).
  34. P. Weinmeister, Ed., J. ?. Poggendorff’s Biographisch-Literarisches Handwo?rterbuch, Vol. 5, Verlag Chemie: Leipzig, 1925, p 906.
  35. E. Noelting, Rudolf Nietski 1847-1917. Helvetica Chimica Acta 1918, 1, 343-430.
  36. J. Fritzsche, Vorläufige Notiz über einige neue Körper aus der lndigoreihe. J. Prakt. Chem. 1843, 28, 198-204.
  37. R. Nietzki, Ueber Anilinschwarz. Ber. Dtsch. Chem. Ges. 1878, 11, 1093-1102.
  38. R. Nietzki, Zur Darstellung der Chinone und Hydrochinone. Ber. Dtsch. Chem. Ges. 1877, 10, 1934-1935.
  39. R. Nietzki, Zur Darstellung des Chinons. Ber. Dtsch. Chem. Ges. 1878, 11, 1102-1104.
  40. A. Bernthsen, Heinrich Caro. Ber. Dtsch. Chem. Ges. 1912, 45, 1987-2042.
  41. A. S. Travis, Heinrich Caro at Roberts, Dale & Co. Ambix 1991, 38, 113-134.
  42. A. Bernthsen, Zum 70. Geburtstage von H. Caro. Z. Angew. Chem. 1911, 24, 1059-1064.
  43. M. Wiedemann, Heinrich Caro. Chem. Ind. 1910, 33, 561.
  44. H. Caro, Die Oxydation des Anilins. Chemiker Zeitung 1896, 20, 840.
  45. H. Caro, Zur Kenntniss der Oxydation des Anilins. Verh. Ges. Dtsch. Naturforsch. Aerzte 1896, 68, 119-120.
  46. R. Willstätter, C. W. Moore, Über Anilinschwarz. I. Ber. Dtsch. Chem. Ges. 1907, 40, 2665–2689.
  47. E. Berl, Richard Willstätter. Chem. Eng. News 1942, 20, 954.
  48. R. Robinson, Richard Willstätter. 1872-1942. Obit. Notices Fellows R. Soc., 1953, 8, 609-634.
  49. R. Robinson, Richard Willstätter. J. Chem. Soc. 1953, 999-1026.
  50. R. Adams, Richard Willstätter. J. Am. Chem. Soc. 1943, 65, 127-128.
  51. R. Huisgen, Richard Willstätter. J. Chem. Educ. 1961, 38, 10-15.
  52. R. Willstätter, S. Dorogi, Über Anilinschwarz. II. Ber. Dtsch. Chem. Ges. 1909, 42, 2147–2168.
  53. H. Th. Bucherer. Über den Mechanismus der Indamin- und Azinsynthese. Bemerkungen zu der Abhandlung R. Willstätters über Anilinschwarz. Ber. Dtsch. Chem. Ges. 1907, 40, 3412–3419.
  54. R. Willstätter, S. Dorogi, Über Anilinschwarz. III. Ber. Dtsch. Chem. Ges. 1909, 42, 4118–4151.
  55. R. Willstätter, C. Cramer, Über Anilinschwarz. IV. Ber. Dtsch. Chem. Ges. 1910, 43, 2976–2988.
  56. A. G. Green, A. E. Woodhead, Aniline-black and Allied Compounds. Part I. J. Chem. Soc. Trans. 1910, 97, 2388-2403.
  57. A. G. Green, The Chemical Technology of Aniline Black. In Seventh International congress of applied chemistry, London, May 27th to June 2nd, 1909. Partridge & Cooper, Ltd.: London, 1910, Sect IVb, pp. 83-84.
  58. A. G. Green, The Chemical Technology of Aniline Black. J. Soc. Dyers Colour. 1909, 25, 188-192.
  59. K. H. Saunders, Arthur George Green. J. Soc. Dyers Colour. 1941, 57, 364-366.
  60. J. Baddiley, Arthur George Green. J. Chem. Soc. 1946, 842-852.
  61. K. H. Saunders, The Scientific and Technical Work of Professor A. G. Green, F.R.S. J. Soc. Dyers Colour. 1944, 60, 81-93.
  62. R. J. Friswell, A. G. Green, On the Relation of Diaxobenaeneanilide to Anzidoazobenzene. J. Chem. Soc., Trans. 1909, 95, 2202-2215.
  63. E. J. Cross, J. B. Speakman, Prof. F. M. Rowe, F.R.S. Nature 1947, 159, 53.
  64. R. Willstätter, C. Cramer, Über Anilinschwarz. V. Ber. Dtsch. Chem. Ges. 1911, 44, 2162–2171.
  65. A. G. Green, A. E. Woodhead, Anilinschwarz und seine Zwischenkorper. II.. Ber. Dtsch. Chem. Ges. 1912, 45, 1955-1958.
  66. A. G. Green, A. E. Woodhead, Aniline-black and Allied Compounds. Part II. J. Chem. Soc. Trans. 1912, 101, 1117-1123.