폴리아닐린의 화학적 중합 시 반응속도에 미치는 양성자산의 영향

홍장후; 장범순; Jang-Hoo Hong; Beom Soon Jang

Journal of the Korean Industrial and Engineering Chemistry, Vol.16, No.5, 684-688, October, 2005

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폴리아닐린의 화학적 중합 시 반응속도에 미치는 양성자산의 영향

Effect of Protonic Acids on the Reaction Rate in Chemical Polymerization of Polyaniline

홍장후 , 장범순^†

서울산업대학교 정밀화학과

Jang-Hoo Hong , and Beom Soon Jang^†

Department of Fine Chemistry, Seoul National Uninversity of Technology, Seoul 139-743, Korea

E-mail:

초록

산도가 각기 다른 양성자산(HF, HCI, HBr, HI, H2SO4)의 수용액내에서 아닐린을 중합하였다. 이때 산도(pH)와 상대이온(counter ion)의 반응성에 따른 반응속도에 관하여 조사하였다. 반응속도에 대한 양성자산의 영향을 조사하기 위하여, open-circuit potential을 측정하였다. 그 결과 HF 수용액내에서 중합속도가 가장 느리게 나타났고, HI 수용액내에서는 중합반응이 진행되지 않았으며, 이러한 결과들을 산도(pH)와 산화력과의 관계로 설명하였다. 양성자산의 종류에 따라 dimer들의 생성비율도 각기 다르게 나타났으며, 이러한 결과들을 상대이온(음이온)의 친핵성도 (nucleophilicity), 용매화효과 및 이동도의 영향으로 설명하였다.

Aniline was polymerized in various protonic acid (HF, HC1, HBr, HI, H2SO4) aqueous solutions with different acidity. During the reaction, the dimer formation and the reaction rate were examined as functions of acidity (pH) and the size of counter ions. Open-circuit potential measurements were carried out to investigate the effect of protonic acid on the reaction rate. The results showed that polymerization rate in HF aqueous solution was very slow and polymerization did not occur in HI aqueous solution. These results were explained in terms of acidity and power of oxidation. The ratio of formation of dimers varied with the kind of protonic acid, and the results were explained with the nucleophilicity, solvation effect, and mobility of counter ions.

Keywords:Polyaniline;open-circuit potential measurement;protonic acid;reaction rate;counter ions

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[Related Articles]

[1] Macdiarmid AG, Epstein AJ, J. Chem. Soc. Faraday Disc., 88, 317 (1989)

[2] Vikki T, Pietila LO, Osterholm H, Ahjopalo L, Takala A, Toivo A, Levon K, Passiniemi P, Ikkala O, Macromolecules, 29(8), 2945 (1996)

[3] Gettinger CL, Heeger AJ, Pine DJ, Cao Y, Synth. Met., 74, 81 (1995)

[4] Yang CY, Heeger AJ, Cao Y, Synth. Met., 79, 27 (1996)

[5] Yue J, Epstein AJ, J. Am. Chem. Soc., 112, 2800 (1990)

[6] Ginder JM, Epstein AJ, Phys. Rev., B, Condens. Matter, 41, 10674 (1990)

[7] Joo J, Epstein AJ, Appl. Phys. Lett., 65, 2278 (1994)

[8] Diaz AF, Bargon JA, J. Electroanal. Chem., 111, 112 (1980)

[9] MacDiarmid AG, Epstein AJ, Synth. Met., 69, 85 (1994)

[10] Tzou K, Gregory RV, Synth. Met., 47, 267 (1992)

[11] Lux F, Polymer, 35(14), 2915 (1994)

[12] Morales GM, Llusa M, Miras MC, Barbero C, Polymer, 38(20), 5247 (1997)

[13] Kang ET, Neoh KG, Tan KL, Wong HK, Synth. Met., 48, 231 (1992)

[14] Wei Y, Tang X, Sun Y, Focke WW, J. Polym. Sci. A: Polym. Chem., 27, 2385 (1989)

[15] Gill MT, Chapman SE, DeArmitt CL, Baines FL, Dadswell CM, Stamper JG, Lawless GA, Billingham NC, Armes SP, Synth. Met., 93, 227 (1998)

[16] Wei Y, Hsueh KF, Jang GW, Polymer, 35(16), 3572 (1994)

[17] Manohar SK, Macdiarmid AG, Epstein AJ, Synth. Met., 41, 711 (1991)