Pendant Benzo-15-Crown-5를 포함한 Poly(crown Ethers)의 합성과 양이온 결합특성

이종관; 김종향

Polymer(Korea), Vol.15, No.2, 130-140, April, 1991

Export Citation

Pendant Benzo-15-Crown-5를 포함한 Poly(crown Ethers)의 합성과 양이온 결합특성

Synthesis and Cation-Binding Properties of POly(crown Ethers) with pendant Benzo-15-Crown-5

이종관, 김종향

초록

Pendant benzo-15-crown-5를 포함한 acryloyl methyl benzo-15-crown-5 단량체는 4'-hydroxy methyl benzo-15-crown-5와 acryloyl chloride를 반응시켜 합성하였다. Acryloyl methyl benzo-15-crown-5의 단독중합체와 acryloyl methyl benzo-15-crown-5와 ethyl acrylate 공중합체는 AIBN을 개시제로 하여 벤젠 또는 메탄올 용매하에서 제조하였다. 중합체의 양이온 결합 효율은 크라운 에테르를 포함한 유기층과 알카리 과염소산염을 포함한 수용액층으로부터 추출된 수용액층의 양이온의 농도를 용매추출법으로 측정하였다. 그 결과 pendant 크라운 에테르를 포함한 중합체 즉 poly(crown ether)는 단량체보다 양이온의 추출효과가 뛰어남을 볼 수가 있었다. 여러가지 크라운착물의 화학양론 조성비를 전도도법으로 측정하였다. 이러한 측정방법으로 고분자주위에 양이온이 결합하는 최대수를 알 수가 있다.

Acryloyl methyl benzo-15-crown-5 monomer containing pendant benzo-15-crown-5 was synthesized by reacting 4'-hydroxy methyl benzo-15-crown-5 with acryloyl chloride. The homopolymer of acryloyl methyl benzo-15-crown-5 and its copolymer with ethyl acrylate were prepared in benzene or methanol by using AIBN as an initiator. The cation binding efficiencies of the polymers were evaluated by the extraction of the cation in aqueous phase between aqueous phase and an immiscible organic phase (methylene chloride). The results showed that the polymers containing pendant crown ether moieties, so-called poly(crown ether)s were more effective in the extraction of the cation than the corresponding monomer. The stoichiometries of the various crown complexes were determined from conductance measurements. These measurements also provide information on the maximum number of the cation that can be bound per polymer molecule.

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[1] Pedersen CJ, J. Am. Chem. Soc., 89, 7017 (1967)

[2] Izatt RM, Christensen JJ, Synthetic Multidentate Macrocyclic Comp., Acad., Press, New York, N.Y. (1979)

[3] San DJ, Simmons HE, J. Am. Chem. Soc., 94, 4024 (1972)

[4] Lamb JD, Christensen JJ, Oscarson JL, Nielson BL, Asay BW, Izatt RM, J. Am. Chem. Soc., 102, 6820 (1980)

[5] Cram DJ, Cram JM, Science, 183, 803 (1972)

[6] Christensen JJ, Eatough DJ, Izatt RM, Chem. Rev., 74, 351 (1974)

[7] Yagi K, Ruiz JA, Sanchez MC, Makromol. Chem. Rapid Commun., 1, 263 (1980)

[8] Wong KH, Yagi K, Smid J, J. Membr. Boil., 18, 379 (1974)

[9] Kimura K, Maeda T, Shono T, Makromol. Chem., 182, 1579 (1981)

[10] Kimura K, Tamura H, Maeda T, Shono T, Polym. Bull., 1, 403 (1979)

[11] Anzai J, Ueno A, Suzuki Y, Osa T, Makromol. Chem. Rapid Commun., 3, 55 (1982)

[12] Kopolow S, HogenEsch TE, Smid J, Macromolecules, 6, 133 (1973)

[13] Shah SC, Kopolow S, Smid J, J. Polym. Sci. A: Polym. Chem., 14, 2023 (1976)

[14] Perrin DD, Armarego WLF, Purification of Laboratory Chemical, 3rd p. 175, Pergamon Press, Australia (1988)

[15] Smid J, ElHaj B, Majewicz T, Nonai A, Sinta R, Org. Prep. Proc. Int., 8, 193 (1976)

[16] Varma AJ, Majewicz T, Smid J, J. Polym. Sci. A: Polym. Chem., 17, 1573 (1979)

[17] Shirai M, Orikata T, Tanaka M, J. Polym. Sci. A: Polym. Chem., 23, 463 (1985)

[18] Fuoss RM, Accasina F, Electrolytic Conductance Interscience (1959)

[19] Takeda Y, Bull. Chem. Soc. Jpn., 54, 3133 (1981)

[20] Pedersen CJ, Frensdroff HK, Angew. Chem.-Int. Edit., 11, 16 (1972)

[21] Frensdorff HK, J. Am. Chem. Soc., 93, 4684 (1971)

[22] Shim JH, Chung KB, Chung EH, Chang SH, Polym.(Korea), 12(1), 63 (1988)

[23] Sinta R, Lamb JD, Smid J, Macromolecules, 16, 1382 (1983)

[24] Koltz IM, Walker FM, Divan RB, J. Am. Chem. Soc., 68, 1486 (1946)

[25] Kimura K, Maeda T, Shono T, Talanta, 26, 945 (1979)