폴리알킬티오펜 유도체의 합성

이창진; 이서봉; 김경중; 주혁종

Polymer(Korea), Vol.19, No.5, 692-699, September, 1995

Export Citation

폴리알킬티오펜 유도체의 합성

Synthesis of Polyalkylthiophene Derivatives

이창진, 이서봉, 김경중, 주혁종

초록

프로판오익산과 티에닐에탄올로부터 티에닐에틸 프로판오에이트(TEP)츨 합성한 뒤 이를 산화중합시켜 에스테르기가 측쇄에 치환되어 있는 폴리(3-프로판오일옥시에틸티오펜)(PPET)을 합성하였다. 그리고 TEP와 3-옥틸티오펜과의 공중합체도 합성하였다. 이와 같이 합성된 폴리알킬티오펜 유도체들은 무게평균분자량이 40,000g/mo1에서 70,000g/mo1 정도로 나타났으며 클로로포름이나 테트라히드로퓨란 등에 녹아 폴리옥틸티오펜과 유사한 가공성을 보였다. 공중합체의 NMR분석으로 옥틸티오펜과 에스테르가 치환된 티오펜의 조성비는 임의로 조절이 가능함을 알 수 있었으며 조성비에 따른 공중합체의 유리전이온도(T_g)는 옥틸티오펜의 함량이 증가할수록 감소하였다. 에스테르가 치환된 폴리알킬티오펜 유도체는 폴리옥틸티오펜과 비교하여 최대흡광도(λ_max)가 짧은 파장쪽으로 이동함을 보였으며 고분자내의 에스테르기가 치환된 티오펜이 증가할수록 고분자 필름의 결정성은 감소함을 보였다. 이는 고분자 필름의 평면적구조가 에스테르기의 도입으로 방해를 받아 이중결합의 공액성이 감소함으로 설명할 수 있다. 또한 산화제이철로 도핑된 폴리알킬 에스테르티오펜 필름의 전기전도도는 폴리옥틸티오펜에 비해 감소함을 보였다.

The oxidation polymerization of 2-(3-thienyl)ethyl propanoate (TEP), which was prepared from propanoic acid and 2-(3-thienyl)ethanol, produced poly(3-propanoyl-oxyethylthiophene) (PPET) with the ester group in the side chain. TPS was also copolymerized with 3-octylthiophene to produce the corresponding copolymers. The prepared polymers had the weight average molecular weight between 40,000 g /mol and 70,000 g /mol and were soluble in THF and CHCl₃. The NMR analysis of the copolymers showed that the content ratio of 3-octylthiophene and the ester substituted thiophene can be tailored. As the content of 3-octylthiophene unit in the copolymers increased, the glass transition temperature (T_g)decreased. Compared with poly(octylthiophene), polyalkylthiophenes with ester group in the side chain exhibited blue shift of UV absorption maxima and decrease of crystallinity due to the pertubation of chain ordering. The electrical conductivities of the doped polymer film decreased as the content of ester substituted unit in the polymers increased.

[References]

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Diaz AF, Kanazawa KK, Gardini GPJ, J. Chem. Soc.-Chem. Commun., 635 (1979)
Sato M, Tanaka S, Kaeriyama K, J. Chem. Soc.-Chem. Commun., 873 (1986)
Jen KY, Miller GG, Elsenbaumer RL, J. Chem. Soc.-Chem. Commun., 1346 (1986)
Hotta S, Rughooputh SDDV, Heeger AJ, Wudl F, Macromolecules, 20, 212 (1987)
Sugimoto R, Takeda S, Yoshino K, Chem. Express, 1, 635 (1986)
Chang AC, Blankespoor RL, Miller LL, J. Electroanal. Chem., 236, 239 (1987)
Tanaka S, Sato MA, Kaeriyama K, Synth. Met., 25, 277 (1988)
Feldhues M, Kampf G, Litterer H, Mecklenburg T, Wegener P, Synth. Met., 2, C487 (1989)
Patil AO, Ikenoue Y, Basescu N, Colaneri N, Wudl F, Heeger AJ, Synth. Met., 20, 151 (1988)
Coche L, Deronzier A, Moutet JC, J. Electroanal. Chem., 198, 187 (1986)
Mao H, Xu B, holdcroft S, Macromolecules, 26, 1163 (1993)
Andreani F, Bizzari PC, Costa CD, Salatelli E, Polym. Bull., 27, 117 (1991)
Lee CJ, Kim KY, Rhee SB, Mol. Cryst. Liq. Cryst., 247, 31 (1994)
Lee C, Kim KJ, Rhee SB, Synth. Met., 69, 295 (1995)
Kang TJ, Kim JY, Kim KJ, Lee C, Rhee SB, Synth. Met., 69, 377 (1995)
Tomao K, Kodama S, Nakajima I, Kumada M, Minato A, Suzuki S, Tetrahedron, 38, 3347 (1982)
Pomerantz M, Tseng JJ, Zhu H, Sproull SJ, Reynolds JR, Unitz R, Arnott HJ, Haider MI, Synth. Met., 32, 825 (1991)
Hotta S, Soga M, Sonoda N, Synth. Met., 26, 267 (1988)
McCullough RD, Tristram-Nagle S, William SP. Lowe RD, Jayaraman M, J. Am. Chem. Soc., 115, 4910 (1993)
Yoshino K, Nakajima S, Fujii S, Sugimoto RI, Polym. Commun., 28, 309 (1987)
Yoshino K, Nakajima S, Sugimoto K, Jpn. J. Appl. Phys., 26, L1038 (1987)
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Berggren M, Gustafsson G, Inganas O, Andersson MR, Wennerstrom O, Hjertberg T, Adv. Mater., 6, 488 (1994)

[Referenced By]

[1] Tourillon G, "Handbook of Conducting Polymers," ed. by T.a. Skotheim, vol. 1, p. 293-350, Marcel Dekker, New York (1986)

[2] Diaz AF, Kanazawa KK, Gardini GPJ, J. Chem. Soc.-Chem. Commun., 635 (1979)

[3] Sato M, Tanaka S, Kaeriyama K, J. Chem. Soc.-Chem. Commun., 873 (1986)

[4] Jen KY, Miller GG, Elsenbaumer RL, J. Chem. Soc.-Chem. Commun., 1346 (1986)

[5] Hotta S, Rughooputh SDDV, Heeger AJ, Wudl F, Macromolecules, 20, 212 (1987)

[6] Sugimoto R, Takeda S, Yoshino K, Chem. Express, 1, 635 (1986)

[7] Chang AC, Blankespoor RL, Miller LL, J. Electroanal. Chem., 236, 239 (1987)

[8] Tanaka S, Sato MA, Kaeriyama K, Synth. Met., 25, 277 (1988)

[9] Feldhues M, Kampf G, Litterer H, Mecklenburg T, Wegener P, Synth. Met., 2, C487 (1989)

[10] Patil AO, Ikenoue Y, Basescu N, Colaneri N, Wudl F, Heeger AJ, Synth. Met., 20, 151 (1988)

[11] Coche L, Deronzier A, Moutet JC, J. Electroanal. Chem., 198, 187 (1986)

[12] Mao H, Xu B, holdcroft S, Macromolecules, 26, 1163 (1993)

[13] Andreani F, Bizzari PC, Costa CD, Salatelli E, Polym. Bull., 27, 117 (1991)

[14] Lee CJ, Kim KY, Rhee SB, Mol. Cryst. Liq. Cryst., 247, 31 (1994)

[15] Lee C, Kim KJ, Rhee SB, Synth. Met., 69, 295 (1995)

[16] Kang TJ, Kim JY, Kim KJ, Lee C, Rhee SB, Synth. Met., 69, 377 (1995)

[17] Tomao K, Kodama S, Nakajima I, Kumada M, Minato A, Suzuki S, Tetrahedron, 38, 3347 (1982)

[18] Pomerantz M, Tseng JJ, Zhu H, Sproull SJ, Reynolds JR, Unitz R, Arnott HJ, Haider MI, Synth. Met., 32, 825 (1991)

[19] Hotta S, Soga M, Sonoda N, Synth. Met., 26, 267 (1988)

[20] McCullough RD, Tristram-Nagle S, William SP. Lowe RD, Jayaraman M, J. Am. Chem. Soc., 115, 4910 (1993)

[21] Yoshino K, Nakajima S, Fujii S, Sugimoto RI, Polym. Commun., 28, 309 (1987)

[22] Yoshino K, Nakajima S, Sugimoto K, Jpn. J. Appl. Phys., 26, L1038 (1987)

[23] Xai B, Holdcroft S, Macromolecules, 26, 4457 (1993)

[24] Berggren M, Gustafsson G, Inganas O, Andersson MR, Wennerstrom O, Hjertberg T, Adv. Mater., 6, 488 (1994)