가용성, 혼합 구조의 폴리페닐렌 합성에 있어서의 부반응

조재동; 김대흠; 김광웅; 김정안

Polymer(Korea), Vol.18, No.1, 7-13, January, 1994

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가용성, 혼합 구조의 폴리페닐렌 합성에 있어서의 부반응

The Side Reactions in Synthesis of Soluble and Mixed Structure Polyphenylene

조재동, 김대흠, 김광웅, 김정안

초록

유기용제에 가용성이며 적절한 전기전도도를 갖는 폴리페닐렌을 Wurtz coupling reaction을 통하여 단량체를 1,4-dibromobenzene과 개시제로 n-butyllithium을 사용하여 반응조건을 변화시키면서 합성하였다. 이 때 발생하는 부반응에 대하여 spectroscopy를 통하여 조사한 결과 main chain의 phenyl ring에 f-butyl기의 attachment와 THF와의 부반응이 발생하여 부산물인 n-butyl branch를갖는 폴리페닐렌이 합성되었다. Phenyl ring에 attachment된 n-butyl기의 양은 52.9%∼8.20%였다.

Polyphenylene having not only solubility in organic solvents but electrical conductivity was prepared by using n-butyllithium as a initiator and 1,4-dibromobenzene as a monomer through the Wurtz coupling reaction under a variety of the reaction conditions. Spectroscopic analysis provided an information about side reactions generating n-butyl branch in the phenyl ring of the main chain as well as hydroxy group resulting from the reaction of organolithium with tetrahydrofuran. The amounts of n-butyl branch attached on the pheny1 ring were 52.9% ∼8.20%.

[References]

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[1] Ivory DM, Miller GG, Sowa JM, Shacklette LW, Chance RR, Baughman RH, J. Chem. Phys., 71(3), 1506 (1979)

[2] Kovacic P, Wu G, J. Polym. Sci., 47, 45 (1960)

[3] Kovacic P, Kyriakis A, J. Am. Chem. Soc., 85, 454 (1963)

[4] Kovacic P, Oziomek J, J. Org. Chem., 29, 100 (1964)

[5] Yamamoto T, Hayashi Y, Yamamoto A, Bull. Chem. Soc. Jpn., 51, 2091 (1978)

[6] Dellamar M, Lacaze PC, Dumousseau JY, Dumois JE, Electrochim. Acta, 27(1), 61 (1977)

[7] Fauvarque JF, Digua A, Petit MA, Savard J, Makromol. Chem., 186, 2415 (1985)

[8] Ballard D, Courtis A, Shirley I, Taylor S, Macromolecules, 21, 294 (1988)

[9] Chaturvedi V, Tanaka S, Kaeriyama K, Macromolecules, 26, 2607 (1993)

[10] Marvel CS, Hartzell GE, J. Am. Chem. Soc., 81, 448 (1959)

[11] Baughman RH, Bredas JL, Chance RR, Elsenbaumer RL, Shacklette LW, Chem. Rev., 82, 209 (1982)

[12] Jones MB, Kovacic P, Lanska D, J. Polym. Sci. A: Polym. Chem., 19, 89 (1981)

[13] Rehahn M, Schulter AD, Wegner G, Feast WJ, Polymer, 30, 1054 (1989)

[14] Zhong XF, Francois B, Makromol. Chem. Rapid Commun., 9, 411 (1988)

[15] Tour JM, Stephens EB, Davis JF, Macromolecules, 25, 499 (1992)

[16] Tour JM, Private Communication

[17] Tour JM, Stephens EB, J. Am. Chem. Soc., 113, 2309 (1991)

[18] Gillman H, Langham W, Moore FW, J. Am. Chem. Soc., 62, 2327 (1940)

[19] March J, Advanced Organic Chemistry: 4th Ed. Wiley-Interscience, New York, p. 499 (1992)

[20] Brandsma L, Verkruijsse HD, Preparative Polar Organometallic Chemistry: Springer-Verlag: Berlin, Vol. 1, p. 26 (1987)

[21] Stephens EB, Kinsey KE, Davis JF, Tour JM, Macromolecules, 26, 3519 (1993)

[22] Nentwig W, Sinn S, Makromol. Chem. Rapid Commun., 1, 59 (1980)