Micro-Chemical Structure of Polyaniline Synthesized by Self-Stabilized Dispersion Polymerization

Hyun Namgoong; Dong Jin Woo; Suck-Hyun Lee

Macromolecular Research, Vol.15, No.7, 633-639, December, 2007

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Micro-Chemical Structure of Polyaniline Synthesized by Self-Stabilized Dispersion Polymerization

Hyun Namgoong, Dong Jin Woo¹, and Suck-Hyun Lee^{1, †}

Kolon Central Research Park, Mabukri, Guseongeup, Youngin City 449-797, Korea
¹Department of Molecular Science and Technology, Ajou University, Suwon 443-749, Korea

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A variety of NMR techniques were applied to the micro-chemical structural characterization of polyanilines prepared via an efficient synthetic method in a self-stabilized dispersion medium in which the polymerization was conducted in a heterogeneous organic/aqueous biphasic system without any stabilizers. Here, the monomer and growing polymer chain were shown to function simultaneously as a stabilizer, imparting compatibility for the dispersion of the organic phase, and as a form of flexible template in an aqueous reaction medium. Polymerizations predicated on this concept generated polyanilines with a low defect content: solution state 13C-NMR and solid 13C DD/CP/MAS spectroscopy indicated that the synthesized HCPANi and its soluble derivative, HCPANi-t-BOC, evidenced distinctly different NMR spectra with fewer side peaks, as compared to conventionally prepared PANis, and the complete structural assignments of the observed NMR peaks could be determined via the combination of both 1D and 2D techniques. Ortho-linked defects in HCPANi were estimated to be as low as 7%, as shown by a comparison of the integration of the carbonyl carbon resonance peaks.

Keywords:polyaniline;self-stabilized dispersion polymerization;NMR characterizations;chemical microstructure

[References]

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Huang WS, Humphrey BD, MacDiarmid AG, J. Chem. Soc.-Faraday Trans., 8, 2385 (1986)
Lee SH, Lee DH, Lee K, Lee CW, Adv. Funct. Mater., 15(9), 1495 (2005)
Lee CW, Seo YH, Lee SH, Macromolecules, 37(11), 4070 (2004)
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Raghunathan A, Ranbarajan G, Trivedi DC, Synth. Met., 81, 39 (1996)
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Ashraf SA, Kanemaguire LA, Majidi MR, Pyne SG, Wallace GG, Polymer, 38(11), 2627 (1997)
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Yasuda A, Shimidzu T, Synth. Met., 61, 239 (1993)
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[Referenced By]

[1] Wallace GG, Spinks GM, Kane-Maguire LAP, Teasdale PR, in Conductive Electroactive Polymers, CRC Press, New York, 2003, pp 51

[2] Epstein AJ, in Organic Electronic Materials, R. Farchini and G. Gross, Eds., Springer, Berlin, 2001, pp 3

[3] Wessling B, in Handbook of Nanostructured Materials and Nanotechnology, H. S. Nalwa, Ed., Academic Press, San Diego, 2000, pp 501

[4] Macdiarmid AG, Chiang JC, Halpern M, Huang WS, Mu SL, Somasiri NL, Wu W, Yaniger SI, Mol. Cryst. Liq. Cryst., 121, 173 (1985)

[5] Huang WS, Humphrey BD, MacDiarmid AG, J. Chem. Soc.-Faraday Trans., 8, 2385 (1986)

[6] Lee SH, Lee DH, Lee K, Lee CW, Adv. Funct. Mater., 15(9), 1495 (2005)

[7] Lee CW, Seo YH, Lee SH, Macromolecules, 37(11), 4070 (2004)

[8] Kaplan S, Conwell EM, Richter AF, MacDiarmid AG, J. Am. Chem. Soc., 110, 7647 (1988)

[9] MacDiarmid AG, Chiang JC, Richter AF, Somarisi NLD, Epstein AJ, in Conducting Polymers, L. Alcacer, Ed., D. Reidel, Dordrecht, 1987, pp 105

[10] Yasuda A, Shimidzu T, Synth. Met., 61, 239 (1993)

[11] Armes SP, in Handbook of Conducting Polymers, T. A. Skotheim, R. L. Elsenbaumer, and J. R. Reynolds, Eds., 2nd, Marcel Dekker, New York, 1998, pp 423

[12] Huang JX, Virji S, Weiller BH, Kaner RB, J. Am. Chem. Soc., 125(2), 314 (2003)

[13] Huang JX, Kaner RB, J. Am. Chem. Soc., 126(3), 851 (2004)

[14] Huang J, Kaner RB, Angew. Chem.-Int. Edit., 43, 5817 (2004)

[15] Jang J, Ha J, Kim S, Macromol. Res., 15(2), 154 (2007)

[16] Mallick K, Witcomb MJ, Scurrell MS, Gold Bulletin, 39, 166 (2006)

[17] Spetseris N, Ward RE, Meyer TY, Macromolecules, 31(9), 3158 (1998)

[18] Louie J, Hartwig JF, Macromolecules, 31(19), 6737 (1998)

[19] Sadighi JP, Singer RA, Buchwald SL, J. Am. Chem. Soc., 120(20), 4960 (1998)

[20] Fyfe CA, in Solid State NMR for Chemists, C. F. C Press, Guelph, Ontario (1983)

[21] Mehring M, Principles of High Resolution, NMR in Solids, Springer-Verlag, Berlin (1983)

[22] Raghunathan A, Ranbarajan G, Trivedi DC, Synth. Met., 81, 39 (1996)

[23] Stejskal EO, Memory JD, High Resolution NMR in the Solid State, Oxford Press, New York (1994)

[24] Kenwright AM, Feast WJ, Adams P, Milton AJ, Monkman AP, Say BJ, Polymer, 33, 4292 (1992)

[25] Heeger AJ, Rev. Mod. Phys., 73, 681 (2001)

[26] Epstein AJ, in Organic Electronic Materials, R. Farchini and G. Gross, Eds., Springer, Berlin, 2001, pp 3

[27] Ashraf SA, Kanemaguire LA, Majidi MR, Pyne SG, Wallace GG, Polymer, 38(11), 2627 (1997)

[28] Zhang XX, Sadighi JP, Mackewitz TW, Buchwald SL, J. Am. Chem. Soc., 122(31), 7606 (2000)

[29] Lee K, Cho S, Park SH, Heeger AJ, Lee CW, Lee SH, Nature, 441, 65 (2006)

[30] Adams PN, Apperley DC, Monkman AP, Polymer, 34, 328 (1993)

[31] Ward RE, Meyer TY, Macromolecules, 36(12), 4368 (2003)

[32] Yasuda A, Shimidzu T, Synth. Met., 61, 239 (1993)

[33] Sahoo SK, Nagarajan R, Roy S, Samuelson LA, Kumar K, Cholli AL, J. Am. Chem. Soc., 37, 4130 (2004)

[34] Goddard YA, Vold RL, Hoatson GL, Macromolecules, 36(4), 1162 (2003)

[35] Young TL, Espe MP, Yang D, Mattes BR, Macromolecules, 35(14), 5565 (2002)

[36] Mathew R, Yang DL, Mattes BR, Espe MP, Macromolecules, 35(20), 7575 (2002)

[37] Zagorska M, Pron A, Lefrant S, Handbook of Organic Conductive Molecules and Polymers, H. S. Nalwa, Ed., Jhon Wiley & Sons, New York, 1997, Chap. 4, pp 190