가교 폴리(4-비닐피리딘)-구리(Ⅱ) 착물에 의한 Ascorbic Acid의 산화반응 2. 가교제의 영향

이석기; 서재곤; 구광모; 전일련; 김우식; Suk-Kee Lee; Jae-Kon Suh; Kwang-Mo Koo; In-Ryon Jeon; Woo-Sik Kim

Polymer(Korea), Vol.24, No.2, 252-258, March, 2000

Export Citation

가교 폴리(4-비닐피리딘)-구리(Ⅱ) 착물에 의한 Ascorbic Acid의 산화반응 2. 가교제의 영향

Oxidation of AScorbic Acid by Crosslinked Poly(4-vinyl pyridine)-Cu(Ⅱ) Complexes 2. Effect of Crosslinker

이석기, 서재곤¹, 구광모, 전일련, 김우식^{1, †}

경일대학교 공업화학과
¹경북대학교 고분자공학과

Suk-Kee Lee, Jae-Kon Suh, Kwang-Mo Koo, In-Ryon Jeon, and Woo-Sik Kim^†

Department of Polymer Science, Kyungpook National Univ., Taegu 702-701, Korea

E-mail:

초록

4-비닐피리딘과 N,N''-1,6-헥사메틸렌비스아크릴아미드를 라디칼중합하여 여러 가지 가교도를 가지는 가교 폴리(4-비닐피리딘) (CHP4VP)을 합성하였고, 이들 가교고분자와 구리(Ⅱ)와의 착물을 평형흡착법으로 제조하였다. 제조한 착물들을 ascorbic acid(AA)의 산화반응 촉매로 사용하여 촉매활성을 조사하였다. CHP4VP-Cu(Ⅱ) 착물에 의한 AA 산화반응은 MichaelisMenten형 동력학적 거동을 나타내었다. CHP4VP-Cu(Ⅱ) 촉매계의 촉매활성은 CHP4VP의 가교도가 증가할수록 증가하였고, 또 CHP4VP-Cu(Ⅱ) 착물은 재사용 후에도 촉매활성이 거의 감소하지 않았다. 그러나 CHP4VP-Cu(Ⅱ) 착물은 전보의 N,N''-메틸렌비스아크릴아미드가 가교제로 포함된 가교 폴리(4-비닐피리딘)-구리(Ⅱ) 착물보다 AA산화반응에 대한 촉매활성이 감소하는 경향을 나타내었다. 이들 결과로부터 촉매계에 포함된 CHP4VP의 가교도와 가교계의 소수성이 AA 산화반응에 중요한 역할을 함을 알 수 있었다.

Various crosslinked poly(4-vinylpyridines) (CHP4VP) having different degrees of crosslinking were synthesized by radical copolymerization fo 4-vinylpyridine with N,N''-1,6-hexamethylenebisacrylamide, and CHP4VP-Cu(Ⅱ) complexes were perpared by the method of adsorption equilibrium. The catalytic activity of the complexes for the oxidation of ascorbic acid (AA) was investigated. The oxidation of AA by these complexes showed a kinetic activity of CHP4VP-Cu(Ⅱ) complexes was decreased for the oxidation of AA when compared with that of the previously reported catalytic system containing crosslinked poly(4-vinylpyridine) prepared using N,N''-methylenebisacrylamide as crosslinker. These results indicate that the degree of crosslinking of CHP4VP and the hydrophobicity of the crosslinker play an important role in the catalytic system of the oxidation of AA.

Keywords:crosslinked poly(4-vinylpyridine);degree of crosslinking;ascorbic acid;catalytic activity;hydrophobicity

[References]

Saegusa T, Hirai H, Tsuchida E, "Polymer-Metal Complexes," Kagaku Do-Jin, Kyoto, 1978 (1978)
Gebelein CG, Charraher CE, "Bioactive Polymeric Systems," Plenum Press, New York, 1985 (1985)
Takemoto K, Inaki Y, Ottenbrite RM, "Functional Monomers and Polymers," Marcel Dekker Inc., New York, 1987 (1987)
Guyot A, Hodge P, Shemington DC, Widdecke H, React. Polym., 16, 233 (1991)
Agnew NH, J. Polym. Sci. A-Polym. Chem., 14, 2819 (1976)
Carlini C, Sbrana G, J. Macromol. Sci.-Chem., A16, 323 (1981)
Ran R, J. Polym. Sci. A-Polym. Chem., 31, 1561 (1993)
Niside H, Deguchi J, Tsuchida E, Bull. Chem. Soc. Jpn., 49, 3498 (1976)
Tsuchida E, Nishikawa H, Terada E, J. Polym. Sci. A-Polym. Chem., 14, 825 (1976)
Skurlatov Y, Kovner VY, Travin SO, Kirsh YE, Purmal AP, Kabanov VA, Eur. Polym. J., 15, 811 (1979)
Yamashita K, Susuki OY, Tsuda K, Macromol. Chem. Rapid Commun., 9, 705 (1988)
Yamashita K, Kanamori T, Nango M, Tsuda K, Polymer, 34, 2638 (1993)
Miyagi A, Nishitama S, Tsuruya S, Masai M, J. Mol. Catal., 55, 379 (1989)
Henry PM, Ma X, Noronha G, Zaw K, Inorg. Chim. Acta, 240, 205 (1995)
Zaw K, Henry PM, J. Mol. Catal., 101, 187 (1995)
Egawa H, Nonaka T, Kozakura M, Bull. Chem. Soc. Jpn., 55, 3536 (1982)
Kim WS, Lee SK, Nam KY, Koo KM, Lee GJ, Park BK, Polym.(Korea), 22(6), 1020 (1998)
Kim WS, Lee SK, Seo KH, Macromol. Chem. Phys., 195, 449 (1994)
Lee SK, Kim WS, J. Korean Ind. Eng. Chem., 8(6), 1054 (1997)
Lineweaver H, Burk D, J. Am. Chem. Soc., 56, 658 (1934)
Lee SK, Seo KH, Kim WS, Polymer, 34, 2392 (1993)
Lee SK, Kim WS, Polym.(Korea), 21(5), 725 (1997)

[Referenced By]

[1] Saegusa T, Hirai H, Tsuchida E, "Polymer-Metal Complexes," Kagaku Do-Jin, Kyoto, 1978 (1978)

[2] Gebelein CG, Charraher CE, "Bioactive Polymeric Systems," Plenum Press, New York, 1985 (1985)

[3] Takemoto K, Inaki Y, Ottenbrite RM, "Functional Monomers and Polymers," Marcel Dekker Inc., New York, 1987 (1987)

[4] Guyot A, Hodge P, Shemington DC, Widdecke H, React. Polym., 16, 233 (1991)

[5] Agnew NH, J. Polym. Sci. A-Polym. Chem., 14, 2819 (1976)

[6] Carlini C, Sbrana G, J. Macromol. Sci.-Chem., A16, 323 (1981)

[7] Ran R, J. Polym. Sci. A-Polym. Chem., 31, 1561 (1993)

[8] Niside H, Deguchi J, Tsuchida E, Bull. Chem. Soc. Jpn., 49, 3498 (1976)

[9] Tsuchida E, Nishikawa H, Terada E, J. Polym. Sci. A-Polym. Chem., 14, 825 (1976)

[10] Skurlatov Y, Kovner VY, Travin SO, Kirsh YE, Purmal AP, Kabanov VA, Eur. Polym. J., 15, 811 (1979)

[11] Yamashita K, Susuki OY, Tsuda K, Macromol. Chem. Rapid Commun., 9, 705 (1988)

[12] Yamashita K, Kanamori T, Nango M, Tsuda K, Polymer, 34, 2638 (1993)

[13] Miyagi A, Nishitama S, Tsuruya S, Masai M, J. Mol. Catal., 55, 379 (1989)

[14] Henry PM, Ma X, Noronha G, Zaw K, Inorg. Chim. Acta, 240, 205 (1995)

[15] Zaw K, Henry PM, J. Mol. Catal., 101, 187 (1995)

[16] Egawa H, Nonaka T, Kozakura M, Bull. Chem. Soc. Jpn., 55, 3536 (1982)

[17] Kim WS, Lee SK, Nam KY, Koo KM, Lee GJ, Park BK, Polym.(Korea), 22(6), 1020 (1998)

[18] Kim WS, Lee SK, Seo KH, Macromol. Chem. Phys., 195, 449 (1994)

[19] Lee SK, Kim WS, J. Korean Ind. Eng. Chem., 8(6), 1054 (1997)

[20] Lineweaver H, Burk D, J. Am. Chem. Soc., 56, 658 (1934)

[21] Lee SK, Seo KH, Kim WS, Polymer, 34, 2392 (1993)

[22] Lee SK, Kim WS, Polym.(Korea), 21(5), 725 (1997)