폴리이타코네이트계 이중 측쇄 이온 전도성 고분자의 제조 및 전기적 성질

문성인; 공명선

Polymer(Korea), Vol.22, No.5, 699-707, September, 1998

Export Citation

폴리이타코네이트계 이중 측쇄 이온 전도성 고분자의 제조 및 전기적 성질

Preparation and Electrical Properties of Double-Comblike Polyitaconate Ion Conducting Polymers

문성인, 공명선

초록

새로운 종류의 고체 고분자 전해질을 제조하기 위해서 bis[2-(2-methoxyethoxy)ethyl]itaconate 단량체는 itaconic acid와 2-(2-methoxyethoxy)ethanol을 에스테르화 반응에 의하여 합성하였다. 고체 고분자 전해질들은 bis(MEE)itaconate의 단일중합체 그리고 MMA와의 5/1, 3/1 그리고 1/1의 조성을 가지는 공중합체로 제조하였으며 짧은 ethylene oxide 단위가 이중으로 이타코네이트 단위에 붙어있다. 중합체 및 알칼리염 복합체들의 용융 및 유리전이온도 등을 조사하였으며, 공중합체들의 기계적 성질 및 열적 성질은 공중합체 중 MMA의 함량에 따라서 변화하였다. 알칼리염으로서 LiClO₄를 사용하여 단일중합체 및 공중합체로부터 복합체를 제조하였으며 그 혼합비는 [EO]/[Li⁺]=10/1, 8/1 그리고 6/1이다. 고체 고분자 전해질로부터 얻어진 이온전도도는 단일중합체에서 나타났으며 상온에서 6.2*10^-5S/cm의 전도도로서 전형적인 PEO보다 10배 이상 향상됨을 보여주었다.

Bis[2-(2-methoxyethoxy)ethyl]itaconate (Bis(MEE)itaconate) monomer was prepared by the esterification reaction of itaconic acid with 2-(2-methoxyethoxy)ethanol for a new solid polymer electrolyte. The solid polymer electrolytes are based on the copolymers of itaconate and MMA (itaconate/MMA=1/0, 5/1, 3/1 and 1/1) and possess double-comblike pendant short ethylene oxide unit on to an itaconate molecular unit. The thermal behaviors such as melting and glass transition temperature of polymers and lithium salt complexes were investigated. The mechanical strengthes and thermal properties of copolymers changed with an increase of the content of MMA. The homopolymer and copolymers are complexed with LiClO₄ salt at the ratio of [EO]/[Li⁺]=10/1, 8/1 and 6/1. The maximum conductivity was observed at the homopolymer, and the conductivity value obtained from our study was 6.5 x 10^-5 S/cm, an order of magnitude higher than that of classical PEG-based polymer electrolyte at ambient temperature.

Keywords:ion conducting polymer;solid polymer electrolyte;polyitaconate;poly(itaconate-co-MMA);double-comblike polymer

[References]

Binks AE, Sharples A, J. Polym. Sci. A: Polym. Chem., 6, 407 (1968)
Fenton DE, Parker JE, Wright PV, Polymer, 14, 589 (1973)
Wright PV, Br. Polym. J., 7, 319 (1975)
Fauteux D, Robitaille C, J. Electrochem. Soc., 133, 315 (1986)
MacCallum JR, Vincent CA, "Polymer Electroyte Reviews I & II," Elsevier Applied Science, New York (1987)
Baugham RH, Bredas JL, Cgance RR, Eckhardt H, Elsenbaumer RL, Ivory DM, Miller GC, Preiziosi AF, Schacklette LW, "Conductive Polymers," p. 137, Plenum Publ. Corp., New York (1981)
Killis A, LeNest JF, Candini A, Cheradame H, Macromolecules, 17, 63 (1984)
Killis A, LeNest JF, Gandini A, Cheradame H, Macromol. Chem., 183, 2835 (1982)
Nakamura H, Seno M, Sato T, J. Polym. Sci. A: Polym. Chem., 35(1), 153 (1997)
Allcock HR, Austin PE, Neenan TX, Sisko JT, Blonsky PM, Shriver DF, Macromolecules, 19, 1508 (1986)
Blonsky PM, Shriver DF, Austin PE, Allcock HR, J. Am. Chem. Soc., 106, 6854 (1984)
Fish D, Kahn IM, Wu E, Smid J, Br. Polym. J., 20, 281 (1988)
Kobayashi N, Hamada T, Ohno H, Tsuchida E, Polym. J., 18, 661 (1986)
Inoue K, Nishikawa Y, Tanigaki T, J. Am. Chem. Soc., 113, 7609 (1991)
Cowie JMG, Martin ACS, Firth AM, Br. Polym. J., 20, 247 (1988)
Cowie JMG, Martin ACS, Firth AM, Polymer, 28, 627 (1987)
Coltrain BK, Ferrar WT, Salva JM, J. Polym. Sci. A: Polym. Chem., 31, 2261 (1993)

[Referenced By]

[1] Binks AE, Sharples A, J. Polym. Sci. A: Polym. Chem., 6, 407 (1968)

[2] Fenton DE, Parker JE, Wright PV, Polymer, 14, 589 (1973)

[3] Wright PV, Br. Polym. J., 7, 319 (1975)

[4] Fauteux D, Robitaille C, J. Electrochem. Soc., 133, 315 (1986)

[5] MacCallum JR, Vincent CA, "Polymer Electroyte Reviews I & II," Elsevier Applied Science, New York (1987)

[6] Baugham RH, Bredas JL, Cgance RR, Eckhardt H, Elsenbaumer RL, Ivory DM, Miller GC, Preiziosi AF, Schacklette LW, "Conductive Polymers," p. 137, Plenum Publ. Corp., New York (1981)

[7] Killis A, LeNest JF, Candini A, Cheradame H, Macromolecules, 17, 63 (1984)

[8] Killis A, LeNest JF, Gandini A, Cheradame H, Macromol. Chem., 183, 2835 (1982)

[9] Nakamura H, Seno M, Sato T, J. Polym. Sci. A: Polym. Chem., 35(1), 153 (1997)

[10] Allcock HR, Austin PE, Neenan TX, Sisko JT, Blonsky PM, Shriver DF, Macromolecules, 19, 1508 (1986)

[11] Blonsky PM, Shriver DF, Austin PE, Allcock HR, J. Am. Chem. Soc., 106, 6854 (1984)

[12] Fish D, Kahn IM, Wu E, Smid J, Br. Polym. J., 20, 281 (1988)

[13] Kobayashi N, Hamada T, Ohno H, Tsuchida E, Polym. J., 18, 661 (1986)

[14] Inoue K, Nishikawa Y, Tanigaki T, J. Am. Chem. Soc., 113, 7609 (1991)

[15] Cowie JMG, Martin ACS, Firth AM, Br. Polym. J., 20, 247 (1988)

[16] Cowie JMG, Martin ACS, Firth AM, Polymer, 28, 627 (1987)

[17] Coltrain BK, Ferrar WT, Salva JM, J. Polym. Sci. A: Polym. Chem., 31, 2261 (1993)