N-치환 측쇄를 갖는 폴리에테르 폴리우레탄 특성에 대한 측쇄 농도의 효과

이용근; 권정욱; 노시태; Yong Kuen Lee; Jung Ohk Keon; Si Tae Noh

Journal of the Korean Industrial and Engineering Chemistry, Vol.12, No.1, 94-98, February, 2001

Effect of the Side Chain Concentration on the Properties N-substituted Poly(ethylene oxide) Polyurethane with Oligo(ethylene oxide)

이용근, 권정욱, 노시태 ^†

한양대학교 화학공학과, 안산 425-791

Yong Kuen Lee, Jung Ohk Keon, and Si Tae Noh^†

Department of Chemical Engineering, Hanyang University, Ansan 425-791, Korea

E-mail:

초록

측쇄형 고체 고분자 전해질의 특성에 미치는 측쇄 함량의 영향을 연구하기 위하여 올리고에틸렌옥사이드 측쇄의 함량이 각각 0%, 35%, 65%, 및 95%인 N-치환 폴리에틸렌옥사이드 폴리우레탄(N-치환PEOPU)을 합성하였다. 합성된 N-치환 PEOPU의 구조는 적외선 분광 분석기 (FT-IR)와(1) H 핵자기 공명 분광 분석기((1)H-NMR)로 확인하였다. 열적특성은 시차주사열분석기(DSC)와 열 중량 분석(TGA)으로 측정하였다. AC impedance analyzer을 이용하여 N-치환 PEOPU계 고체 고분자 전해질의 이온전도도를 염농도의 함수로 측정하였다. 올리고에틸렌옥사이드 측쇄의 농도가 증가할수록 유리전이온도(T(g))가 감소하였다. 이는 올리고에틸렌옥사이드 측쇄가 PEOPU내에서 내부 가소제 역할을 하여 사슬의 유동성이 증가하기 때문이다. TGA결과로부터 N-치환 PEOPU은 PEOPU 보다 높은 온도에서 분해 반응이 진행되었으며, 메틸기 치환보다는 올리고에틸렌옥사이드 치환체의 함량이 95%인 Me0_(EO)7 95의 경우가 열 안정성이 낮음을 알 수 있었다. 올리고에틸렌옥사이드 측쇄의 함량이 65%인 Me35_(EO)7 65의 이온전도도가 30 ℃, 70 ℃에서 각각 5.9×10(-5), 4.4×10(-3)로 가장 높게 나타났다.

In order to study the effect of short polyether side chain contents on the properties of solid polymer electrolytes (SPE), which were based on a N-substituted PEOPU a series of N-substituted poly(ethylene oxide) polyurethane (N-sub PEOPU) with methyl of oligo (ethylene oxide) having different oligo (ethylene oxide) contents of substituents (0%, 35%, 65%, and 95%) were synthesized. Structure of the synthesized, N-sub PEOPU, was identified using fourier transform infrared spectrometer (FT-IR) and (1)H nuclear magnetic resonance spectroscopy ((1)H-NMR). Thermal properties were measured by a differential scanning calorimeter (DSC) and a thermogravimetric analyzer (TGA). Ion-conductivity was measured as a function of salt concentration using an AC impedance analyzer. The glass transition temperature (T(g)) was gradually decreased to low temperature by increasing the contents of short polyether side chain concentration in N-sub PEOPU. The results of TGA showed that the thermal decomposition of N-sub PEOPU occurred at a higher temperature than PEOPU, and N-oligo(ethylene oxide) PEOPU, Me()_(EO)7 95, showed a lower thermal stability than that of N-methyl PEOPU. The highest conductivity of 5.9×10(-5) at 30 ℃ and 4.4×10(-3) at 70 ℃ was observed for Me35_(EO)7 65.

Keywords:Polyether polyurethane;Solid polymer eletrolytes;N-substituted polyurethane;Ionic conductivity;Thermal property

[References]

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Gray FM, Solid Polymer Electrolytes, VCH Publishers, New York (1991)
Scrosati B, Chapman, and Hall, (3) Application of Electroactive Polymers, London (1993)
Pei Q, Yang Y, Yu G, Zhang C, Heeger AJ, J. Am. Chem. Soc., 118(16), 3922 (1996)
Kono M, Furuta K, Mori S, Watanabe M, Ogata N, Polym. Adv. Technol., 85, 4 (1993)
Watanabe M, Nishimoto A, Solid State Ion., 79, 306 (1995)
Motogami K, Kono M, Mori S, Watanabe M, Electrochim. Acta, 37, 1725 (1992)
Kono M, Hayashi E, Watanabe M, J. Electrochem. Soc., 145(5), 1521 (1998)
Yoon S, Ichikawa K, Macknight WJ, Hsu SL, Macromolecules, 28(14), 5063 (1995)
Bannister DJ, Davies GR, Ward IM, Mcintyre JE, Polymer, 25, 1600 (1984)
Cowie JMG, Martin ACS, Polymer, 28, 627 (1987)
Xia DW, Soltz D, Smid J, Solid State Ion., 14, 221 (1984)
Blonsky PM, Shriver DF, Austin P, Allcock HR, Solid State Ion., 18-19, 258 (1986)
Miller JA, Cooper SL, J. Polym. Sci. B: Polym. Phys., 23, 1065 (1985)
Sivriev H, Georgiev S, Borissov G, Eur. Polym. J., 26, 73 (1990)
Midroyannids JA, J. Polym. Sci. A: Polym. Chem., 22, 891 (1984)
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Takayanagi M, Tikatayose, J. Polym. Sci. A: Polym. Chem., 19, 1133 (1981)
Espenschied B, Schulz RC, Polym. Bull., 5, 489 (1981)
Cairns TL, Foster HD, Larchar AW, Schneider AK, Schreiber RS, J. Am. Chem. Soc., 71, 651 (1949)
Beachell HC, Ngoc Son CP, J. Appl. Polym. Sci., 8, 1089 (1964)
Kashani HA, Barrie JA, Gourge MH, J. Polym. Sci. A: Polym. Chem., 16, 533 (1978)
Beachell HC, Buck JCP, J. Polym. Sci., 7, 1873 (1969)
Foti P, Maravigna, Montaudo G, J. Polym. Sci. A: Polym. Chem., 19, 1679 (1981)
Ballistreri A, Foti S, Maravigna P, Montaudo G, Scamporrino E, J. Polym. Sci. A: Polym. Chem., 18, 1923 (1980)
Cowie JMG, Martin ACS, Polym. Commun., 26, 298 (1985)

[Related Articles]

[1] MacCallum JR, Vincent CA, Polymer Electrolyte Reviews 1 and 2 Eds., Elsevier London (1987)

[2] Gray FM, Solid Polymer Electrolytes, VCH Publishers, New York (1991)

[3] Scrosati B, Chapman, and Hall, (3) Application of Electroactive Polymers, London (1993)

[4] Pei Q, Yang Y, Yu G, Zhang C, Heeger AJ, J. Am. Chem. Soc., 118(16), 3922 (1996)

[5] Kono M, Furuta K, Mori S, Watanabe M, Ogata N, Polym. Adv. Technol., 85, 4 (1993)

[6] Watanabe M, Nishimoto A, Solid State Ion., 79, 306 (1995)

[7] Motogami K, Kono M, Mori S, Watanabe M, Electrochim. Acta, 37, 1725 (1992)

[8] Kono M, Hayashi E, Watanabe M, J. Electrochem. Soc., 145(5), 1521 (1998)

[9] Yoon S, Ichikawa K, Macknight WJ, Hsu SL, Macromolecules, 28(14), 5063 (1995)

[10] Bannister DJ, Davies GR, Ward IM, Mcintyre JE, Polymer, 25, 1600 (1984)

[11] Cowie JMG, Martin ACS, Polymer, 28, 627 (1987)

[12] Xia DW, Soltz D, Smid J, Solid State Ion., 14, 221 (1984)

[13] Blonsky PM, Shriver DF, Austin P, Allcock HR, Solid State Ion., 18-19, 258 (1986)

[14] Miller JA, Cooper SL, J. Polym. Sci. B: Polym. Phys., 23, 1065 (1985)

[15] Sivriev H, Georgiev S, Borissov G, Eur. Polym. J., 26, 73 (1990)

[16] Midroyannids JA, J. Polym. Sci. A: Polym. Chem., 22, 891 (1984)

[17] Tesoro GC, J. Polym. Sci. Macromol. Rev., 13, 339 (1978)

[18] Takayanagi M, Tikatayose, J. Polym. Sci. A: Polym. Chem., 19, 1133 (1981)

[19] Espenschied B, Schulz RC, Polym. Bull., 5, 489 (1981)

[20] Cairns TL, Foster HD, Larchar AW, Schneider AK, Schreiber RS, J. Am. Chem. Soc., 71, 651 (1949)

[21] Beachell HC, Ngoc Son CP, J. Appl. Polym. Sci., 8, 1089 (1964)

[22] Kashani HA, Barrie JA, Gourge MH, J. Polym. Sci. A: Polym. Chem., 16, 533 (1978)

[23] Beachell HC, Buck JCP, J. Polym. Sci., 7, 1873 (1969)

[24] Foti P, Maravigna, Montaudo G, J. Polym. Sci. A: Polym. Chem., 19, 1679 (1981)

[25] Ballistreri A, Foti S, Maravigna P, Montaudo G, Scamporrino E, J. Polym. Sci. A: Polym. Chem., 18, 1923 (1980)

[26] Cowie JMG, Martin ACS, Polym. Commun., 26, 298 (1985)