고분자 반응을 이용한 Maleic anhydride계 비선형 광학 고분자의 합성 및 전기광학 특성

박이순; 금창대; 송재원; 김광택; 김기현; 강신원

Journal of the Korean Industrial and Engineering Chemistry, Vol.9, No.5, 704-709, October, 1998

Synthesis and Properties of Nonlinear Optical Polymer Derived from α-Methyl Styrene/Maleic Anhydride by Polymer Reaction

박이순, 금창대, 송재원, 김광택, 김기현, 강신원

초록

α-Methyl styrene과 maleic anhydride를 공단량체로 사용하여 유리전이온도가 높고 내열성이 우수한 poly (α-methylstyrene-co-maleic anhydride) (MSMA) 기재 고분자 (substrate polymer)를 합성하고 여기에 니트로기를 가진 발색단을 고분자반응을 이용하여 도입하는 반응 및 생성된 비선형 광학 고분자의 전기 광학 특성에 대해 조사하였다. MSMA 기재 고분자에 hydroxyl기를 가지는 azo계 발색단 (chromophore) 2-[4-(4-nitrophenylazo)-N-ethylphenylamino]ethanol (DR1)을 고분자 반응 (polymer reaction)으로 maleic anhydride에 ester 결합으로 도입할 때 4-dimethylaminopyridine (DMAP) 촉매만을 쓴 것 (MSMA-D)보다 DMAP와 3-dicyclohexyl carbodiimid (DCC)를 동시에 사용한 경우 (MSMA-DC)가 DR1 발색단의 도입율이 높게 나타났다. 비선형 광학 고분자 (MSMA-DC)의 전기광학계수 (r₃₃)는 파장이 632.8 nm인 광원에서 18 pm/V의 값을 나타냈으며 열적 안정성도 유리전이 온도 (T_g)가 175℃ 이상으로 우수하게 나타났다.

Non-linear optical polymer based on poly (α-methylstyrene-co-maleic anhydride) (MSMA) substrate polymer was prepared by polymer reaction method and its thermal and electro-optic properties were examined. In the polymer reaction between MSMA substrate polymer and 2-[4-(4-nitrophenylazo)-N-ethylphenylamino]ethanol (DR1) chromophore, the degree of substitution of DR1 into MSMA was higher with the 4-dimethylaminopyridine (DMAP) as catalyst and 3-dicyclohexyl carbodiimid (DCC) as dehydrating agent (sample, MSMA-DC) than the one with just 4-dimethylaminopyridine as catalyst (sample, MSMA-D). The synthesized NLO polymer (MSMA-DC) exhibited electro-optic coefficient of 18 pm/V (632.8 nm) and glass transition temperature (T_g) of about 175℃.

Keywords:Nonlinear Optical Polymer;Poly(α-methylstyrene-co-maleic anhydride);NLO Properties;NLO Polymer Synthesis

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[1] Heeger A, Orenstein J, Ulrich D, "Nonlinear Optical Properties of Polymers," Proc. MRS 10 (1988)

[2] Khanarian G, "Nonlinear Optical Properties of Organic Materials III," Proc. SPIE 1227 (1990)

[3] Williams DJ, "Nonlinear Optical Properties of Organic Materials," ASC Symp. Ser. No. 233 (1983)

[4] Marden S, Sohn J, Stucky G, "Materials for Nonlinear Optics," ACS Symp. Ser, No. 455 (1991)

[5] Tripathy S, Cavicchi E, Kumar J, Kumar R, Chem. Tech., 620 (1989)

[6] Leslie T, Demartino R, Choe E, Khanarian G, Haas D, Yoon H, Mol. Cryst. Liq. Cryst., 153, 451 (1987)

[7] Prasad P, Willams D, "Introdution to NLO Effects in Molecules & Polymers," John Wiley & Sons, NY (1991)

[8] Man H, Yoon H, Adv. Mater., 4, 159 (1992)

[9] Teng CC, Appl. Phys. Lett., 60, 1538 (1992)

[10] Song K, Mortazavi M, Yoon H, ACS Symp. Series No. 601, Chap. 24, 333 (1995)

[11] Odian G, "Principles of Polymerization," McGraw-Hill (1970)

[12] Drost KJ, Jen AKY, Rao VP, ChemTech., Sep., 16 (1995)

[13] Song K, Kim N, Mol. Cryst. Liq. Cryst., 280, 11 (1996)

[14] Mcculloch I, Man HT, Song K, Yoon H, J. Appl. Polym. Sci., 53(5), 665 (1994)

[15] Teng CC, Man HT, Appl. Phys. Lett., 56, 1734 (1990)

[16] Park LS, Kim GH, Ha KR, Chang JG, Polym.(Korea), 17(4), 372 (1993)