Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 31108
Heterophase Polymerization of Pyrrole and Thienyl End Capped Ethoxylated Nonyl Phenol by Iron (III) Chloride

Authors: Görkem Ülkü, Esin A. Güvel, Nesrin Köken, Nilgün Kızılcan


This study presents synthesis of novel block copolymers of thienyl end capped ethoxylated nonyl phenol and pyrrole via chemical oxidative polymerization. Ethoxylated nonyl phenol (ENP) was reacted with 2-thiophenecarbonyl chloride in order to synthesize a macromonomer containing thienyl end-group (ENPThC). Then copolymers of ENP-ThC and pyrrole were synthesized by chemical oxidative polymerization using iron (III) chloride as an oxidant. ENP-ThC served both as a macromonomer and an emulsifier for pyrrole with poor solubility in water. The synthesized block copolymers (ENP-ThC-b-PPy) were characterized by spectroscopic analysis and the electrical conductivities were investigated with 4-point probe technique.

Keywords: polypyrrole, end capped polymer, heterophase polymerization, ethoxylated nonyl phenol

Digital Object Identifier (DOI):

Procedia APA BibTeX Chicago EndNote Harvard JSON MLA RIS XML ISO 690 PDF Downloads 2098


[1] D.C. Trivedi, in: H.S. Nalwa (Ed.), Handbook of Organic Conductive Molecules and Polymers, vol. 2, Wiley, New York, 1997.
[2] J. Rodriguez, H.J. Grande, T.F. Otero, in: H.S. Nalwa (Ed.), Handbook of Organic Conductive Molecules and Polymers, vol. 2, Wiley, New York, 1997.
[3] N. Nugay, Z. Kucukyavuz, S. Kucukyavuz, “Conductive properties of poly(4-vinylpyridine)-poly(dimethylsiloxane) block copolymers doped with tetracyanoquinodimethane” Polymer, Vol. 34, Issue 22, 1993, pp. 4649-4654.
[4] G. Cakmak, Z. Kucukyavuz, S. Kucukyavuz, H. Cakmak, “Mechanical, electrical and thermal properties of carbon fiber reinforced poly(dimethylsiloxane)/polypyrrole composites” Compos. Part A: Appl. Sci. Manufact. Vol. 35(4), 2004, pp. 417-421.
[5] M.Ozyalcın, Z. Kucukyavuz, “Synthesis, characterization and electrical properties of iodinated poly(N-vinylimidazole)” Synth. Met. Vol. 87(2), 1997, pp. 123- 126.
[6] P. Yıldırım, Z. Kucukyavuz, “Synthesis and characterization of conducting polypyrrole-cis-1,4-polybutadiene composites” Synth. Met. Vol. 95(1), 1998, pp. 17- 22.
[7] M. Sankır, Z. Kucukyavuz, S. Kucukyavuz, “Synthesis and characterization of poly(dimethylsiloxane)–polythiophene composites”, J. Appl. Poly. Sci. Vol. 87(13), 2003, pp. 2113- 2119.
[8] G.Cakmak, Z.Kucukyavuz, S.Kucukyavuz, “Conductive copolymers of polyaniline,polypyrrole and poly(dimethylsiloxane)” Synthetic Met. Vol.151, 2005, pp. 10-18.
[9] A. Shimizu, K. Yamaka, M. Kohno, “Rechargeable lithium batteries using polypyrrole-poly(styrenesulfonate) composite as the cathodeactive material”, Bulletin of the Chemical Society of Japan, Vol. 61, 1988, pp. 4401–4406.
[10] G. Sotzing, J.R. Reynolds, P. Steel, '' Electrochromic conducting polymers via electrochemical polymerization of bis(2-(3,4- ethylenedioxy)thienyl) monomers'', Chemistry of Materials, Vol. 8, 1996, pp. 882–889.
[11] D. Braun, A. Heeger, “Visible light emission from semiconducting polymer diodes'', Applied Physics Letters, Vol. 58, 1991, pp. 1982–1984.
[12] F. Larmat, J.R. Reynolds, “Polypyrrole as a solid electrolyte for tantalum capacitors”, Synthetic Metals, Vol. 79, 1996, pp. 229–233.
[13] F. Selampinar, L. Toppare, U. Akbulut, T. Yalcin, S. Suzer, “A conducting composite of polypyrrole II, As a gas sensor”, Synthetic Metals, Vol. 68, 1995, pp. 109–116.
[14] R. Martin, W. Liang, V. Menon, R. Parthasarathy, A. Parthasarathy, “Electronically conductive polymers as chemically-selective layers for membrane-based separations”, Synthetic Metals, Vol. 57, 1993, pp. 3766–3773.
[15] F. Selampinar, U. Akbulut, M.Y. Ozden, L. Toppare, “Immobilization of invertase in conducting polymer matrices”, Biomaterials, Vol. 18, 1997, pp. 1163–1168.
[16] R. Singh, R.P. Tandon, V.S. Panwar, S. Chandra, “Low frequency ac conduction in lightly doped polypyrrole films”, Journal of Applied Physics, Vol. 69, 1991, pp. 2504- 2511.
[17] K. Veluri, J. Corish, D.A. Morton-Blake, F. Beniere, “A lattice simulation of the migration of the BF4− ion in polythiophene and polypyrrole lattices” J. Molecular Structure: Theochem, Vol. 365(1), 1996, pp. 13- 19.
[18] K. Veluri, J. Corish, D.A. Morton-Blake, F. Beniere, “A lattice simulation investigation of the migration of chloride ions in doped polypyrrole and polythiophene”, J. Molecular Structure: Theochem, Vol. 334, 1995, pp. 109- 120.
[19] J. Corish, D.A. Morton-Blake, K. Veluri, F. Beniere, “Atomistic simulations of the structures of the pristine and doped lattices of polypyrrole and polythiophene”, J. Molecular Structure: Theochem Vol. 283, 1993, pp. 121- 134.
[20] L.A. Samuelson, M.A.’’ Kinetics of the degradation of electrical conductivity in polypyrrole’’, Druy, Macromolecules, Vol.19, 1986 pp:824-828.
[21] D.T. Glatzhofer, J. Ulanski, G. Wegner, “Controlled conductivity behaviour in poly(p-styrenesulphonate) salts of polypyrrole”, Polymer Vol. 28, 1987, pp. 449- 453.
[22] I.Sultana, M.M.Rahman, S.Li, J.Wang, C.Wang, G.G.Wallace, H.Liu, ''Electrodeposited polypyyrole(PPy)/para(toluene sulfonic acid)(pTS) free-standing film for lithium secondary battery application '' Journal of Electrochimica Acta Vol. 60, 2005, pp.201-205.
[23] K.C. Khulbe and R.S. Mann, ‘’ Polymerization of pyrrole by potassium persulfate’’ Journal of Polymer Chemistry., Vol.20, 1982, pp. 1089- 1095.
[24] V. Bocchi, L. Chierici and G.P. Gardini, ‘’ On pyrrole oxidation with hydrogen peroxide’’ Tetrahedron, Vol.26 (1970) 4073-4082.
[25] R.E. Myers, ‘’ Chemical oxidative polymerization as a synthetic route to electrically conducting polypyrroles’’ Journal of Electronic Materials, Vol.15 (1986) pp. 61-69
[26] S. Machida, S. Miyata and A. Techagumpuch, ‘’ Chemical synthesis of highly electrically conductive polypyrrole’’ Synthetic Metals, Vol.31 (1989) pp. 311-318.
[27] J.A. Walker, L.F. Warren and E.F. Witucki,’’ New chemically prepared conducting pyrrole blacks’’ Journal of Polyrner Chemistry., Vol.26 (1988) pp.1285-1294.
[28] S. Rapi, V. Bocchi and G.P. Gardini, ‘’ Conducting polypyrrole by chemical synthesis in water’’ Synthetic Metals., Vol.24 (1988) pp.217- 221.
[29] N.Kizilcan, B.Ustamehmetoglu, N.Oz, A.Akar, '' Soluble and conductive polypyrrole copolymers containing silicone tegomers'' Journal of Applied Polymer Sci., Vol.89, (2003) pp.2896-2901
[30] T. Ozturk and I. Cakmak,’’ Synthesis of Block Copolymers via Redox
[31] Polymerization Process: A Critical Review’’ Iranian Polymer Journal. Vol.16, (2007) pp.561-581
[32] N. Kızılcan and B. Ustamehmetoğlu, ‘’ Chemical Polymerization of Pyrrole in the Presence of Ketone-Formaldehyde Resin’’ Journal of Applied Polymer Science.Vol. 96 (2005) pp.618-624.
[33] M.M. Castillo-Ortega, M.B. Inoue and M. Inoue, ‘’ Chemical synthesis of highly conducting polypyrrole by the use of copper(II) perchlorate as an oxidant’’ Syntetic. Metals., Vol. 28 (1989) pp.65-70.
[34] E.T. Kang, K.G. Neoh and H.C. Ti, ‘’ Electrical properties of chemically synthesized polypyrrole-halogen charge transfer complexes ‘’ Solid State Cornmunications., 60 (1986) pp. 457-459.
[35] E.T. Kang, K.G. Neoh, T.C. Tan and Y.K. Ong, ‘’ Electrical and thermal stability of chemically synthesized conductive polypyrrole-halogen complexes’’ Journal of Polymer Degradation and Stability., Vol. 21 (1988) pp. 93-103.
[36] D.Stanke, M.L.Hallensleben, L.Toppare, ''Oxidative polymerization of pyrrole with iron chloride in nitromethane'', Synthetic Metals Vol.72 (1995) pp.159-165
[37] C. Q. Wang, G. Zhang, Z. H. Zhang, X. F. Chen, X.Y.Tang, H. M. Tan, “Characterization and properties of amphiphilic block polymer based on poly(ethylene oxide) and poly(butyl acrylate)”, Journal of Applied Polymer Science, Vol.,89 pp.3432-3436.
[38] N. Öz and A. Akar, N. Yılmaz, “Ethoxylated Nonyl Phenols and Ethoxylated Fatty Alcohols–Ceric Ion Redox Systems for Aqueous Polymerization of Vinyl Monomers”. Journal of Applied Polymer Science, Vol.82 (2001) pp.310-313.