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

Abstract:

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: End capped polymer, ethoxylated nonyl phenol, heterophase polymerization, polypyrrole.

Digital Object Identifier (DOI): doi.org/10.5281/zenodo.1099058

References:

[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.