Hydroxy-terminated Poly(propylene carbonate)의 합성

정성미; 문정열; 박대원; 박상욱; 이진국

Journal of the Korean Industrial and Engineering Chemistry, Vol.9, No.2, 273-277, April, 1998

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Hydroxy-terminated Poly(propylene carbonate)의 합성

Synthesis of Hydroxy-terminated Poly(propylene carbonate)

정성미, 문정열, 박대원, 박상욱, 이진국

초록

본 연구는 metal alkoxide, 크라운에테르, 4급 onium염 들을 촉매로 사용하여 프로필렌카보네이트(PC)와 알콜 개시제로부터 hydroxy-terminated poly(propylene carbonate) (HTPPC)를 합성하는데 관한 것이다. 촉매의 종류와 골격구조, 알콜의 종류와 농도, 그리고 용매가 반응에 미치는 영향을 고찰하였다. Metal alkoxide의 Lewis acidity가 크고 alkoxide 음이온의 친핵성이 클수록 높은 반응활성을 나타내었다. Metal alkoxide와 크라운에테르의 혼합촉매는 metal alkoxide 단독 촉매보다 높은 프로필렌 카보네이트 전화율을 보였고, 4급 onium염 촉매의 경우 양이온의 크기가 크고 음이온의 친핵성이 클수록 높은 활성을 나타내었다. 또한 용매의 극성이 높고 [PC]/[Initiator]의 농도 비가 낮을수록 HTPPC의 수율이 높게 나타났다.

The synthesis of hydroxy-terminated poly(propylene carbonate)(HTPPC) was performed by the reaction of propylene cabonate(PC) with alcohol initiator using metal alkoxides, crown ethers and quaternary onium salts as catalysts. The effects of catalyst structure, types and concentration of alcohol, and solvent were investigated. Among the alkoxide catalysts tested, the ones with higher Lewis acidity and with more nucleophilic alkoxide anion showed higher catalytic activity. Mixed catalysts of metal alkoxied and crown ether showed higher conversion of PC than metal alkoxide alone. Quaternary onium salts of bulky cation exhibited higher catalytic activity. High polar solvent showed higher yield of HTPPC and the yield increased with the decrease of [PC]/[Initiator] ratio.

[References]

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[1] Starks CM, Liotta CL, Halpern M, "Phase Transfer Catalysis," Chapman & Hall, N.Y. (1994)

[2] Kihara N, Endo T, J. Polym. Sci. A: Polym. Chem., 31, 2765 (1993)

[3] Kihara N, Hara N, ENdo T, J. Org. Chem., 58, 6198 (1993)

[4] Inoue S, Kobayashi M, Koinuma H, Tsuruta T, Makromol. Chem., 155, 61 (1972)

[5] Kobayashi M, Inoue S, Koinuma M, Tsuruta T, J. Polym. Sci. A: Polym. Chem., 11, 2383 (1973)

[6] Inoue S, Progr. Polym. Sci. Jpn., 1 (1975)

[7] Unoue S, Koinuma H, Tsuruta T, Polym. J., 2, 220 (1971)

[8] Inoue S, Koinuma H, Yokoo Y, Tsuruta T, Makromol. Chem., 143, 97 (1971)

[9] Aida T, Inoue S, Macromolecules, 19, 8 (1986)

[10] Hino Y, Yoshida Y, Inoue S, Polym. J., 16, 159 (1984)

[11] Koinuma H, Hirai H, Makromol. Chem., 178, 1283 (1997)

[12] Vogadanis L, Hoitz W, Makromol. Chem. Rapid Commun., 7, 543 (1986)

[13] European Patent, 93-119220.7 (1993)

[14] Park DW, Moon JY, Yang JG, Lee JK, Energy Conv. Manag., 38, S449 (1997)

[15] Moon JY, Yang JG, Jung SM, Park DW, Lee JK, React. Kinet. Catal. Lett., 61, 315 (1997)

[16] Park DW, Moon JY, Yang JG, Park SH, Lee JK, J. Korean Ind. Eng. Chem., 7(1), 26 (1996)

[17] McGrath JE, "Ring-Opening Polymerization," ACS Symposium Series 286, Washington (1985)