Polypyrrole

Polypyrrole
Pyrrole can be polymerised electrochemically.[1]

Polypyrrole (PPy) is a type of organic polymer formed by polymerization of pyrrole. Polypyrroles are conducting polymers, related members being polythiophene, polyaniline, and polyacetylene.[2] The Nobel Prize in Chemistry was awarded in 2000 for work on conductive polymers including polypyrrole.[3]

Synthesis

Some of the first examples of polypyrroles were reported in 1963 by Weiss and coworkers. These workers described the pyrolysis of tetraiodopyrrole to produce highly conductive materials.[4] Most commonly PPy is prepared by oxidation of pyrrole, which can be achieved using ferric chloride in methanol:

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

Polymerization 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 + x FeCl3 → (C4H2NH)nClx + x FeCl2

The polymerization and p-doping can also be affected electrochemically. The resulting conductive polymer are peeled off of the anode. Cyclic voltammetry and chronocoulometry methods can be used for electrochemical synthesis of polypyrrole.[5]

Properties

Films of PPy are yellow but darken in 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 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 has been discussed as a form of artificial muscle.[6] The surface of polypyrrole films represent fractal properties and ionic diffusion through them show anomalous diffusion pattern.[7][8]

Applications

PPy and related conductive polymers have two main application in electronic devices and for chemical sensors.[9] PPy is also potential vehicle for drug delivery. The polymer matrix serves as a container for proteins.[10]

Research trends

Polypyrrole is also being investigated in low temperature fuel cell technology to increase the catalyst dispersion in the carbon support layers [11] and to sensitize cathode electrocatalysts, as it has been inferred that the metal electrocatalysts (Pt, Co, etc.) when coordinated with the nitrogen in the pyrrole monomers show enhanced oxygen reduction activity.[12]

Polypyrrole (together with other conjugated polymers such as polyaniline, poly(ethylenedioxythiophene) etc.) has been actively studied as a material for "artificial muscles", a technology that would offer numerous advantages over traditional motor actuating elements.[13]

Polypyrrole was used to coat silica and reverse phase silica to yield a material capable of anion exchange and exhibiting hydrophobic interactions.[14]

Polypyrrole was used in the microwave fabrication of multiwalled carbon nanotubes, a new method that allows to obtain CNTs in a matter of seconds.[15]

Chemical and Engineering News reported in June 2013 that Chinese research has produced a water-resistant polyurethane sponge coated with a thin layer of polypyrrole that absorbs 20 times its weight in oil and is reusable.[16]

See also

References

  1. ↑ "Trans IChemE, Part B, Process Safety and Environmental Protection, 2007, 85(B5): 489–493". Enzyme Electrodes for Glucose Oxidation by Electropolymerization of Pyrrole. Retrieved 2009-06-08.
  2. ↑ 2.0 2.1 "Polypyrrole: a conducting polymer; its synthesis, properties and applications" Russ. Chem. Rev. 1997, vol. 66, p.443ff. (http://iopscience.iop.org/0036-021X/66/5/R04)
  3. ↑ A. G. MacDiarmid, ""Synthetic metals": A novel role for organic polymers (Nobel Lecture)", Angew. Chem., Int. Ed. 2001, 40, 2581-2590. doi:10.1002/1521-3773(20010716)40:14<2581::aid-anie2581>3.0.co;2-2
  4. ↑ R. McNeill, R. Siudak, J. H. Wardlaw, D. E. Weiss "Electronic Conduction in PolymersI. The Chemical Structure of Polypyrrole" Aust. J. Chem. 1963, vol. 16, pp. 1056-75. doi:10.1071/CH9631056
  5. ↑ Ahmad Sharifi-Viand, Determination of fractal rough surface of polypyrrole film: AFM and electrochemical analysis, Synthetic metals(Elsevier), 191: 104-112 (2014).
  6. ↑ Ray H. Baughman "Playing Nature's Game with Artificial Muscles "Science 2005, Vol. 308, pp. 63-65. doi:10.1126/science.1099010
  7. ↑ Ahmad Sharifi-Viand, Diffusion through the self-affine surface of polypyrrole film, Vacuum, [doi:10.1016/j.vacuum.2014.12.030]
  8. ↑ Ahmad Sharifi-Viand, Investigation of anomalous diffusion and multifractal dimensions in polypyrrole film, Journal of Electroanalytical Chemistry(Elsevier), 671: 51–57 (2012).
  9. ↑ Janata, Jiri; Josowicz, Mira "Progress Article: Conducting polymers in electronic chemical sensors" Nature Materials (2003), 2(1), 19-24. doi:10.1038/nmat768
  10. ↑ S. Geetha, Chepuri R.K. Rao, M. Vijayan, D.C. Trivedi, "Biosensing and drug delivery by polypyrrole" "Molecular Electronics and Analytical Chemistry Analytica Chimica Acta 2006, Volume 568, Pages 119–125. doi:10.1016/j.aca.2005.10.011
  11. ↑ 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: 100806124255047. doi:10.1021/jp104664t.
  12. ↑ 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. doi:10.1021/jp910572g.
  13. ↑ http://atmsp.whut.edu.cn/resource/pdf/4987.pdf
  14. ↑ http://www.sciencedirect.com/science/article/pii/002196739185003X
  15. ↑ pubs.rsc.org/en/content/articlelanding/2011/CC/C1CC13359D
  16. ↑ Chemical and Engineering News, 26June2013 "Greasy Sponge Slurps Up Oil" http://cen.acs.org/articles/91/web/2013/06/Greasy-Sponge-Slurps-Oil.html