가교 4-비닐피리딘 고분자와 알킬할라이드의 4차화 반응의 속도론적 연구

조영도; 안주현; 임선기

HWAHAK KONGHAK, Vol.34, No.4, 471-476, August, 1996

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가교 4-비닐피리딘 고분자와 알킬할라이드의 4차화 반응의 속도론적 연구

A Kinetic Study on the Quaternization of Cross- linked Poly(4-vinylpyridine) with an Alkyl Halide

조영도, 안주현, 임선기

초록

3%, 5%, 10%의 가교도를 갖는 폴리(4-비닐피리딘) 구형입자를 합성하여, 알킬할라이드와의 4차화 반응에 대하여 연구하였다. 4차화 반응속도는 폴리(4-비닐피리딘)구형입자의 가교도가 증가할수록, 알킬할라이드의 알킬기가 클수록 반응속도는 감소하였으나, 사용된 용매의 극성이 증가할수록 반응속도는 증가하였다. 특히 4차화 반응이 어느 정도 진행된 후에는 반응속도가 급격히 감소하는 것을 알 수 있었으며, 이에 대한 적절한 모델을 제시하였다.

Poly(4-vinylpyridine) resin beads with 3%, 5%, and 10% crosslinkings were prepa- red, and then the quaternization by alkyl halides was investigated. The quaternization rate de- creased with increasing the degree of crosslinking and the size of alkyl halide, however, increased with increasing the dielectric constant of solvent. Particularly the reaction rate steeply decreased as the quaternization more or less proceeded and this phenomenon could be interpreted through the proposed model.

Keywords:Quaternization;Poly(4-vinylpyridine);Alkyl Halide;Degree of Crosslinking

[References]

Adams BA, Holmes EL, J. Soc. Chem. Ind., 54, 1 (1935)
Kronick PL, Fuoss RM, J. Am. Chem. Soc., 77, 6114 (1955)
Hirsch E, Fuoss RM, J. Am. Chem. Soc., 77, 6115 (1955)
Watanabe M, Fuoss RM, J. Am. Chem. Soc., 78, 527 (1956)
Coleman BD, Fuoss RM, J. Am. Chem. Soc., 77, 5472 (1955)
Fuoss RM, Watanabe M, Coleman BD, J. Polym. Sci., 48, 5 (1960)
Tsuchida E, Irie S, J. Polym. Sci. A: Polym. Chem., 11, 789 (1973)
Caryle RM, Chem. Ind., 34, 561 (1982)
Ford WT, Tomoi M, Adv. Polym. Sci., 55, 52 (1984)
Arends CB, J. Chem. Phys., 39, 1903 (1963)
Morcellet-Sauvage J. Loucheux C, Makromol. Chem., 176, 315 (1975)
Boucher EA, Groves JA, Mollett CC, J. Chem. Soc.-Faraday Trans., 73, 1629 (1977)
boucher EA, Khosravi-Babadi E, Mollett CC, J. Chem. Soc.-Faraday Trans., 74, 427 (1978)
Boucher EA, Khosravi-Babadi E, Mollett CC, J. Chem. Soc.-Faraday Trans., 75, 1728 (1979)
Boucher EA, Mollett CC, J. Chem. Soc.-Faraday Trans., 78, 75 (1982)
Frere Y, Gramain P, Macromolecules, 25, 3184 (1992)
Chow LY, Fuoss RM, J. Am. Chem. Soc., 80, 1095 (1958)
Greig JA, Sherrington DC, Polymer, 19, 163 (1978)
Bernard DC, Fuoss RM, J. Am. Chem. Soc., 77, 5472 (1955)
Fuoss RM, Catherts GI, J. Polym. Sci., 4, 97 (1949)
Tamikado T, J. Polym. Sci., 43, 489 (1960)
Crank J, "The Mathematics of Diffusion," 2nd ed., Oxford University Press, Oxford (1956)
Frank-Kamenetskii DA, "Diffusion and Heat Exchange in Chemical Kinetics," 2nd ed., Plenum, New York (1969)

[1] Adams BA, Holmes EL, J. Soc. Chem. Ind., 54, 1 (1935)

[2] Kronick PL, Fuoss RM, J. Am. Chem. Soc., 77, 6114 (1955)

[3] Hirsch E, Fuoss RM, J. Am. Chem. Soc., 77, 6115 (1955)

[4] Watanabe M, Fuoss RM, J. Am. Chem. Soc., 78, 527 (1956)

[5] Coleman BD, Fuoss RM, J. Am. Chem. Soc., 77, 5472 (1955)

[6] Fuoss RM, Watanabe M, Coleman BD, J. Polym. Sci., 48, 5 (1960)

[7] Tsuchida E, Irie S, J. Polym. Sci. A: Polym. Chem., 11, 789 (1973)

[8] Caryle RM, Chem. Ind., 34, 561 (1982)

[9] Ford WT, Tomoi M, Adv. Polym. Sci., 55, 52 (1984)

[10] Arends CB, J. Chem. Phys., 39, 1903 (1963)

[11] Morcellet-Sauvage J. Loucheux C, Makromol. Chem., 176, 315 (1975)

[12] Boucher EA, Groves JA, Mollett CC, J. Chem. Soc.-Faraday Trans., 73, 1629 (1977)

[13] boucher EA, Khosravi-Babadi E, Mollett CC, J. Chem. Soc.-Faraday Trans., 74, 427 (1978)

[14] Boucher EA, Khosravi-Babadi E, Mollett CC, J. Chem. Soc.-Faraday Trans., 75, 1728 (1979)

[15] Boucher EA, Mollett CC, J. Chem. Soc.-Faraday Trans., 78, 75 (1982)

[16] Frere Y, Gramain P, Macromolecules, 25, 3184 (1992)

[17] Chow LY, Fuoss RM, J. Am. Chem. Soc., 80, 1095 (1958)

[18] Greig JA, Sherrington DC, Polymer, 19, 163 (1978)

[19] Bernard DC, Fuoss RM, J. Am. Chem. Soc., 77, 5472 (1955)

[20] Fuoss RM, Catherts GI, J. Polym. Sci., 4, 97 (1949)

[21] Tamikado T, J. Polym. Sci., 43, 489 (1960)

[22] Crank J, "The Mathematics of Diffusion," 2nd ed., Oxford University Press, Oxford (1956)

[23] Frank-Kamenetskii DA, "Diffusion and Heat Exchange in Chemical Kinetics," 2nd ed., Plenum, New York (1969)