측쇄로 아조벤젠 Mesogenic Moiety를 갖는 새로운 광응답성 폴리아세틸렌 유도체의 합성과 성질

오세용; 홍승민; 오성일

Polymer(Korea), Vol.21, No.6, 937-946, November, 1997

Synthesis and Properties of Novel Photoresponsive Polyacetylene derivatives with an Azobenzene Mesongenic Moiety in the Side Group

오세용, 홍승민, 오성일

초록

5-[4-(4'-alkylphenylazo)phenoxyl-1-pentyne(alkyl group : H, pentyl, etc.)과 같은 아조벤젠 액정 moiety를 측쇄로 갖는 새로운 치환 아세틸렌을 합성하여 Ziegler-Natta (Fe( acac)₂-AlEt₃), metathesis(WCl₆, MoCl₅) 및 [Rh(NBD)Cl]₂-Et₃N 촉매를 가지고 중합하였다. 특히 Rh 착체 촉매는 벤젠을 용매로 사용하였을 때 97%의 매우 높은 수율로 cis rich 형태의고분자를 생성하였다. 고분자의 분자량, 구조 빛 열적 성질 등은 GPC, FT-IR, ¹H, ¹³C-NMR, UV-Visible 분광학 장치와 DSC를 사용하여 조사하였다.광현미경을 통해 pentylazobenzene기를 함유한 고분자가 부채꼴 조직을 나타내는 스멕틱 액정상을 가지는 것을 알 수 있었다. 또한 단파장의 자외선 조사시 고분자의 광응답성 특성에관해 조사하였다

We have synthesized novel mono-substituted acetylenes with a liquid crystalline azobenzene moiety in the side group such as 5-[4-(4'-alkylphenylaso) phenoxy]-1-pentyne(alkyl group H, pentyl, etc.) and then polymerized them with Ziegler-Natta(Fe(acac)₃-AIEt₃3), metathesis(WCl₆, MoCl₅), and [Rh(NBD)Cl]₂-Et₃N catalysts. Especially, the Rh complex catalyst containing benzene as a solvent produced a cia rich polymer with an extremely high yield of 97%. Spectroscopic characterizations of all polymers were also carried out in view of molecular weight, structure, and thermal history using GPC, FT-IR, ¹H, ¹³C-NMR, UV- visible, and DSC. Polyacetylene derivative having a pentylazobenzene group showed a smectic liquid crystalline phase with a fan-shaped texture through the Polarizing optical microscope measurement. Also, photoresponsive characteristics of all monomers and polymers upon the irradiation of a UV monochromatic light have been investigated.

Keywords:Ph comolex catalyst;oilyacetylene derivative;thermal history;kiquid crystalline;photoresponsiveness

[References]

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[1] Naarmann H, Theophilou N, Synth. Met., 22, 1 (1987)

[2] Akagi K, Suezaki S, Shirakawa H, Kyotani H, Shimomura M, Tanabe Y, Synth. Met., 28, D1 (1989)

[3] Oh SY, Akagi K, Shirakawa H, Synth. Met., 32, D1 (1989)

[4] Tsukamoto J, Takahashi A, Kawasaki K, Jpn. J. Appl. Phys., 29, 125 (1990)

[5] Oh SY, Oguri F, AkaK, Shirakawa H, J. Polym. Sci. A: Polym. Chem., 31, 781 (1993)

[6] Masuda T, Higashimura T, Adv. Chem. Ser., 224, 35 (1990)

[7] Costa G, "Comprehensive Polymer Science," G. Allen, Ed., Pergamon, Oxford (1989)

[8] Oh SY, Akagi K, Shirakawa H, HWAHAK KONGHAK, 34(1), 70 (1996)

[9] Akagi K, Goto H, Kadokura Y, Shirakawa H, Oh SY, Araya K, Synth. Met., 69, 13 (1995)

[10] Ikeda T, Tsutsumi O, Science, 268(5219), 1873 (1995)

[11] Chen SA, Liao CS, Makromol. Chem. Rapid Commun., 14, 69 (1993)

[12] Natansohn A, Rochon P, Gosselin J, Xie S, Macromolecules, 25, 2268 (1992)

[13] Oh SY, Ezaki R, Akagi K, Shirakawa H, J. Polym. Sci. A: Polym. Chem., 31, 2977 (1993)

[14] Oh SY, Akagi K, Shirakawa H, HWAHAK KONGHAK, 34(2), 154 (1996)

[15] Lecoin D, Hochapfel A, Viovy R, Mol. Cryst. Liq. Cryst., 31, 233 (1975)

[16] Oh SY, Akagi K, Shirakawa H, Macromolecules, 26, 6203 (1993)

[17] Barltrop JA, Coyle JD, "Excited States in Organic Chemistry," p. 322, John Wiley & Sons, Ltd. (1975)

[18] Akiyama H, Akita Y, Kudo K, Ichimura K, Mol. Cryst. Liq. Cryst., 280, 91 (1996)