비닐벤조-크라운 에테르 유도체들의 중합반응과 특성에 관한 연구

이종광; 전영식; 김종향; 조병욱

Polymer(Korea), Vol.18, No.5, 717-726, September, 1994

Export Citation

비닐벤조-크라운 에테르 유도체들의 중합반응과 특성에 관한 연구

A Study on the Polymerization and Characteristics of Vinylbenzo-crown Ether Derivatives

이종광, 전영식, 김종향, 조병욱

초록

Acryloylmethylbenzo-15-crown-5 단량체는 4'-hydroxymethylbenzo-15-crown-5와 acryloyl chloride를 반응시켜 합성하였다. Acryloylmethylbenzo-15-crown-5의 단독중합체와 acrylamide 또는 N-vinyl pyrrolidone과의 공중합체는 AIBN을 개시제로 하여 벤젠용매 하에서 합성하였다. 자유라디칼 반응메카니즘에 의한 acryloylmethylbenzo-15-croen-5의 단독중합 반응 속도는, 벤젠을 용매로 사용하어 60±0.1℃에서 단독중합시켰을때의 중합속도(R_p)는 단량테 농도[M]과 개시제 농도[I]에 대하여 R_p=k_p[M]^0.89[I]0.47의 관계를 나타내었다. 이 단량체의 단독중합 총괄활성차 에너지는 24.6Kca1/mol이었다. 또한 poly(acryloylmethylbenzo-15-crown-5)의 열분석도에 의하면, 420℃에서 ligand인 pendant henzo-15-crown-5의 분해에 의한 발열피이크가 나타났고 435℃ 부근에서 단독중합체의 주사슬이 분해됨을 나타냈다. 또한 acryloylmethylbenzo-15-crown-5 단량체, poly(acryloylmethylbenzo-15-crown-5)단독중합체 그리고 acrylamide 또는 N-vinyl pyrrolidone과의 공중합체들에 대한 양이온 결합특성을 용매추출법으로 측정한 결과, 단량체에 비하여 pendant N-group을 포함하고 있는 공중합체들의 추출효과가 훨씬 뛰어났다.

Acryloylmethylbenzo-15-crown-5 monomer was ,synthesized by reaching 4'-hydroxymethylbenzo-15-crown-5 with acryloyl chloride. The homopolymer of acryloylmethylbenzo-15-crown-5 and its copolymer with acrylamide or N-vinyl pyrrolidone were prepared in benzene by using AIBN as an initiator. From the result on kinetic investigation of the free radical polymerization of acryloylmethylbenzo-15-crown-5 in benzene at 60±0.1℃, a rate eqation of R^p=k^p[M]^0.89[I]^0.47 was obtained. The overall activation energy for the polymerization was found to be 24.6Kcal/mol within the temperature range 50∼70℃. The DSC and TGA thermograms of poly(acryloylmethylbenzo-15-crown-5) showed an exother mic peak for the first degradation of pendant benzo-15-crown-5 as a ligand at about 435℃. The cation binding efficiencies of acryloylmethylbenzo-15-crown-5, poly(acryloylmethylbenzo-15-crown-5) and copolymers of acrylamide or N-vinyl pyrrolidone were evaluated by the extraction method. The results showed that the copolymers containing pendant N-group were more of fective in the extraction of the cation than the corresponding monomer.

Keywords:kinetics;vlnylbenzo-crown ether

[References]

Alfrey T, Chares CP, J. Polym. Sci., 21, 101 (1947)
Lenz RW, Saunders K, Balakrishnan J, J. Am. Chem. Soc., 12, 392 (1979)
Miller A, Szafko J, J. Polym. Sci. A: Polym. Chem., 18, 1177 (1980)
O'Brien JL, Gornick F, J. Am. Chem. Soc., 77, 4757 (1955)
Tsuruta T, Chikanishi K, Makromol. Chem., 73, 231 (1964)
Yamada B, Otsu T, J. Polym. Sci. A: Polym. Chem., 7, 2439 (1969)
Pedersen CJ, J. Am. Chem. Soc., 89, 7017 (1967)
Izatt RM, Christensen JJ, "Synthetic Multidentate Macro-Cyclic Comp.," Acad., Press, New York, N.Y. (1979)
San DJ, Simmons HE, J. Am. Chem. Soc., 94, 4024 (1972)
Lamb JD, Christensen JJ, Izatt RM, J. Am. Chem. Soc., 102, 6820 (1980)
Cram DJ, Cram JM, Science, 183, 803 (1972)
Kopolow S, Hogen TE, Smid J, Macromolecules, 6, 133 (1973)
Shah SC, Smid J, J. Polym. Sci. A: Polym. Chem., 14, 2023 (1976)
Blout ER, Hohenstein WP, "Monomer," p. 35-45, Interscience Pub., N.Y. (1949)
Ponratnam S, Kapur SL, Makromol. Chem., 178, 1029 (1977)
Smid J, Haj B, Sinta R, Org. Prepr. Proc. Int., 8, 193 (1976)
Varma AJ, Smid J, J. Polym. Sci. A: Polym. Chem., 17, 1573 (1979)
Otsu T, Tanaka H, J. Polym. Sci., 13, 2605 (1975)
Parth KJ, Philippovich N, J. Macromol. Sci.-Chem., A11, 1319 (1977)
Ordian G, "Principles of Polymerization," p. 179, McGraw-Hill Book, Co., N.Y. (1970)
Schulz GV, Haborth G, Makromol. Chem., 1, 106 (1948)
Sugiyama K, Lee SW, Makromol. Chem., 178, 421 (1977)
Ueda M, Pittuman CU, J. Polym. Sci. A: Polym. Chem., 24, 3177 (1986)
Diab MA, J. Polym. Sci. A: Polym. Chem., 21, 3249 (1983)

[1] Alfrey T, Chares CP, J. Polym. Sci., 21, 101 (1947)

[2] Lenz RW, Saunders K, Balakrishnan J, J. Am. Chem. Soc., 12, 392 (1979)

[3] Miller A, Szafko J, J. Polym. Sci. A: Polym. Chem., 18, 1177 (1980)

[4] O'Brien JL, Gornick F, J. Am. Chem. Soc., 77, 4757 (1955)

[5] Tsuruta T, Chikanishi K, Makromol. Chem., 73, 231 (1964)

[6] Yamada B, Otsu T, J. Polym. Sci. A: Polym. Chem., 7, 2439 (1969)

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

[8] Izatt RM, Christensen JJ, "Synthetic Multidentate Macro-Cyclic Comp.," Acad., Press, New York, N.Y. (1979)

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

[10] Lamb JD, Christensen JJ, Izatt RM, J. Am. Chem. Soc., 102, 6820 (1980)

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

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

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

[14] Blout ER, Hohenstein WP, "Monomer," p. 35-45, Interscience Pub., N.Y. (1949)

[15] Ponratnam S, Kapur SL, Makromol. Chem., 178, 1029 (1977)

[16] Smid J, Haj B, Sinta R, Org. Prepr. Proc. Int., 8, 193 (1976)

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

[18] Otsu T, Tanaka H, J. Polym. Sci., 13, 2605 (1975)

[19] Parth KJ, Philippovich N, J. Macromol. Sci.-Chem., A11, 1319 (1977)

[20] Ordian G, "Principles of Polymerization," p. 179, McGraw-Hill Book, Co., N.Y. (1970)

[21] Schulz GV, Haborth G, Makromol. Chem., 1, 106 (1948)

[22] Sugiyama K, Lee SW, Makromol. Chem., 178, 421 (1977)

[23] Ueda M, Pittuman CU, J. Polym. Sci. A: Polym. Chem., 24, 3177 (1986)

[24] Diab MA, J. Polym. Sci. A: Polym. Chem., 21, 3249 (1983)