Polypyrrole
Pyrrole can be polymerised electrochemically.[1]

Polypyrrole (PPy) is an organic polymer obtained by oxidative polymerization of pyrrole. It is a solid with the formula H(C4H2NH)nH. It is an intrinsically conducting polymer, used in electronics, optical, biological and medical fields.[2][3]

History

Some of the first examples of PPy were reported in 1919 by Angeli and Pieroni, who reported the formation of pyrrole blacks from pyrrole magnesium bromide.[4] Since then pyrrole oxidation reaction has been studied and reported in scientific literature.

Work on conductive polymers including polypyrrole, polythiophene, polyaniline, and polyacetylene was awarded the Nobel Prize in Chemistry in 2000 to Alan J. Heeger, Alan G. MacDiarmid and Hideki Shirakawa .[5]

Synthesis

Different methods can be used to synthesize PPy, but the most common are electrochemical synthesis and chemical oxidation.[6][3][7]

Chemical oxidation of pyrrole:

n C4H4NH + 2n FeCl3 → (C4H2NH)n + 2n FeCl2 + 2n HCl

The process is thought to occur via the formation of the pi-radical cation C4H4NH+. This electrophile attacks the C-2 carbon of an unoxidized molecule of pyrrole to give a dimeric cation [(C4H4NH)2]++. The process repeats itself many times.

Conductive forms of PPy are prepared by oxidation ("p-doping") of the polymer:

(C4H2NH)n + 0.2 X → [(C4H2NH)nX0.2]

The polymerization and p-doping can also be effected electrochemically. The resulting conductive polymer are peeled off of the anode. Cyclic voltammetry and chronocoulometry methods can be used for electrochemical synthesis of polypyrrole.[8]

Most recent micro and nano droplet researches have been conducted in the synthesis of polypyrrole microstructures using various fluid templates formed on different solid surfaces.[9]

Properties

Films of PPy are yellow but darken in the air due to some oxidation. Doped films are blue or black depending on the degree of polymerization and film thickness. They are amorphous, showing only weak diffraction. PPy is described as "quasi-unidimensional" vs one-dimensional since there is some crosslinking and chain hopping. Undoped and doped films are insoluble in solvents but swellable. Doping makes the materials brittle. They are stable in the air up to 150 °C at which temperature the dopant starts to evolve (e.g., as HCl).[2]

PPy is an insulator, but its oxidized derivatives are good electrical conductors. The conductivity of the material depends on the conditions and reagents used in the oxidation. Conductivities range from 2 to 100 S/cm. Higher conductivities are associated with larger anions, such as tosylate. Doping the polymer requires that the material swell to accommodate the charge-compensating anions. The physical changes associated with this charging and discharging have been discussed as a form of artificial muscle.[10] The surface of polypyrrole films present fractal properties and ionic diffusion through them show anomalous diffusion pattern.[11][12]

Applications

PPy and related conductive polymers have two main application in electronic devices and for chemical sensors and electrochemical applications.[13]

PPy is a potential vehicle for drug delivery. The polymer matrix serves as a container for proteins.[14]

Polypyrrole has been investigated as a catalyst support for fuel cells[15] and to sensitize cathode electrocatalysts.[16]

Together with other conjugated polymers such as polyaniline, poly(ethylenedioxythiophene) etc., polypyrrole has been studied as a material for "artificial muscles", a technology that offers advantages relative to traditional motor actuating elements.[17]

Polypyrrole was used to coat silica and reverse phase silica to yield a material capable of anion exchange and exhibiting hydrophobic interactions.[18]

Polypyrrole was used in the microwave fabrication of multiwalled carbon nanotubes, a rapid method to grow CNT's.[19]

A water-resistant polyurethane sponge coated with a thin layer of polypyrrole absorbs 20 times its weight in oil and is reusable.[20]

The wet-spun polypyrrole fibre can be prepared chemical polymerization pyrrole and DEHS as dopant.[21]

See also

References

  1. ↑ Yu, E.H.; Sundmacher, K. (2007). "Trans IChemE, Part B, Process Safety and Environmental Protection, 2007, 85(B5): 489–493". Enzyme Electrodes for Glucose Oxidation by Electropolymerization of Pyrrole. 85 (5): 489–493. doi:10.1205/psep07031.
  2. 1 2 Vernitskaya, Tat'Yana V.; Efimov, Oleg N. (1997). "Polypyrrole: a conducting polymer; its synthesis, properties and applications". Russ. Chem. Rev. 66 (5): 443–457. Bibcode:1997RuCRv..66..443V. doi:10.1070/rc1997v066n05abeh000261. S2CID 250889925.
  3. 1 2 Müller, D.; Rambo, C.R.; D.O.S.Recouvreux; Porto, L.M.; Barra, G.M.O. (January 2011). "Chemical in situ polymerization of polypyrrole on bacterial cellulose nanofibers". Synthetic Metals. 161 (1–2): 106–111. doi:10.1016/j.synthmet.2010.11.005.
  4. ↑ A. Angeli and A. Pieroni, Qazz. Chim. Ital. 49 (I), 164 (1919)
  5. ↑ MacDiarmid, A. G. (2001). "Synthetic metals: A novel role for organic polymers (Nobel Lecture)". Angew. Chem. Int. Ed. 40 (14): 2581–2590. doi:10.1002/1521-3773(20010716)40:14<2581::aid-anie2581>3.0.co;2-2.
  6. ↑ Sabouraud, Guillaume; Sadki, Saïd; Brodie, Nancy (2000). "The mechanisms of pyrrole electropolymerization". Chemical Society Reviews. 29 (5): 283–293. doi:10.1039/a807124a.
  7. ↑ Rapi, S.; Bocchi, V.; Gardini, G. P. (1988-05-01). "Conducting polypyrrole by chemical synthesis in water". Synthetic Metals. 24 (3): 217–221. doi:10.1016/0379-6779(88)90259-7. ISSN 0379-6779.
  8. ↑ Sharifi-Viand, Ahmad (2014). "Determination of fractal rough surface of polypyrrole film: AFM and electrochemical analysis". Synthetic Metals. 191: 104–112. doi:10.1016/j.synthmet.2014.02.021.
  9. ↑ Johan, Albert (2010). Creating microstructures using conducting polypyrrole. ISBN 9783346068415.
  10. ↑ Baughman, Ray H. (2005). "Playing Nature's Game with Artificial Muscles". Science. 308 (5718): 63–65. doi:10.1126/science.1099010. PMID 15802593. S2CID 180181717.
  11. ↑ Ahmad Sharifi-Viand, Diffusion through the self-affine surface of polypyrrole film Vacuum doi:10.1016/j.vacuum.2014.12.030
  12. ↑ Sharifi-Viand, Ahmad (2012). "Investigation of anomalous diffusion and multifractal dimensions in polypyrrole film". Journal of Electroanalytical Chemistry. 671: 51–57. doi:10.1016/j.jelechem.2012.02.014.
  13. ↑ Janata, Jiri; Josowicz, Mira (2003). "Progress Article: Conducting polymers in electronic chemical sensors". Nature Materials. 2 (1): 19–24. doi:10.1038/nmat768. PMID 12652667. S2CID 1250380.
  14. ↑ Geetha, S.; Rao, Chepuri R.K.; Vijayan, M.; Trivedi, D.C. (2006). "Biosensing and drug delivery by polypyrrole" "Molecular Electronics and Analytical Chemistry". Analytica Chimica Acta. 568 (1–2): 119–125. doi:10.1016/j.aca.2005.10.011. PMID 17761251.
  15. ↑ Unni, Sreekuttan M.; Dhavale, Vishal M.; Pillai, Vijayamohanan K.; Kurungot, Sreekumar (2010). "High Pt Utilization Electrodes for Polymer Electrolyte Membrane Fuel Cells by Dispersing Pt Particles Formed by a Preprecipitation Method on Carbon "Polished" with Polypyrrole". The Journal of Physical Chemistry C. 114 (34): 14654–14661. doi:10.1021/jp104664t.
  16. ↑ Olson, Tim S.; Pylypenko, Svitlana; Atanassov, Plamen; Asazawa, Koichiro; Yamada, Koji; Tanaka, Hirohisa (2010). "Anion-Exchange Membrane Fuel Cells: Dual-Site Mechanism of Oxygen Reduction Reaction in Alkaline Media on Cobalt−Polypyrrole Electrocatalysts". The Journal of Physical Chemistry C. 114 (11): 5049–5059. doi:10.1021/jp910572g.
  17. ↑ "Archived copy" (PDF). atmsp.whut.edu.cn. Archived from the original (PDF) on 21 November 2011. Retrieved 30 June 2022.{{cite web}}: CS1 maint: archived copy as title (link)
  18. ↑ Ge, Hailin; Wallace, G.G. (1991-12-27). "High-performance liquid chromatography on polypyrrole-modified silica". Journal of Chromatography A. 588 (1–2): 25–31. doi:10.1016/0021-9673(91)85003-X.
  19. ↑ pubs.rsc.org/en/content/articlelanding/2011/CC/C1CC13359D
  20. ↑ Chemical and Engineering News, 26June2013 "Greasy Sponge Slurps Up Oil" http://cen.acs.org/articles/91/web/2013/06/Greasy-Sponge-Slurps-Oil.html
  21. ↑ Foroughi, J.; et al. (2008). "Production of polypyrrole fibres by wet spinning". Synthetic Metals. 158 (3–4): 104–107. doi:10.1016/j.synthmet.2007.12.008.
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