금속촉매하 DMT와 EG간 에스테르교환반응

정병옥; 최영주; 김제중; 정석진; 박상순; 이경원

Journal of the Korean Industrial and Engineering Chemistry, Vol.10, No.6, 917-922, October, 1999

Export Citation

금속촉매하 DMT와 EG간 에스테르교환반응

Transesterification of DMT with EG in the Presence of Metal Catalyst

정병옥, 최영주, 김제중, 정석진, 박상순, 이경원

초록

무촉매 또는 촉매 존재하 반응온도 190∼240 ℃에서 DMT와 EG간의 에스테르교환반응을 속도론적으로 살펴 보았다. 반응도는 반응기내에서 계외로 유출된 메탄올의 양을 측정함으로써 계산하였다. 이러한 계외로 유출되는 메탄올로 인한 반응물과 촉매량의 보정을 행하였다. 속도론적인 처리를 한 후 촉매농도, 몰비, 촉매종류, 그리고 온도 의존성에 대하여 살펴보았다. 촉매활성은 Ti>Zn>Sn>Sb의 순이었고 활성화에너지 값은 Zn>Ti>Sn>Sb 순으로 나타났다.

The transesterification of dimethyl terephthalate(DMT) with ethylene glycol(EG) was kinetically investigated in the temperature range from 190 to 240 ℃ with and without a zinc acetate(Zn) as a catalyst. The degree of reaction was calculated by the measurement of the quantity of methanol which distilled from the reaction vessel. The distillation made corrections of reactant and catalyst concentrations necessary. The effects of catalyst concentration, molar ratio of DMT and EG, types of metal compounds, and temperature on kinetics were studied. The catalytic activity of various metal compounds was excellent, in order of Ti, Zn, Sn, and Sb. Also the order of activation energy was Zn>Ti>Sn>Sb.

Keywords:transesterification;degree of reaction;catalytic activity;metal compound activation energy

[References]

Ravindranath K, Mashelkar RA, Chem. Eng. Sci., 41, 2197 (1986)
Ravindranath K, Mashelkar RA, Chem. Eng. Sci., 41, 2969 (1986)
Kotliar AM, J. Polym. Sci. Macromol. Rev., 16, 367 (1981)
양갑승, 최창남, 안계혁, 진성룡, 합성섬유의 고효율 중합(IV), p. 253, 과학기술처 (1991)
Rod V, Diwani GE, Minarik M, Sir Z, Colln. Czech. Chem. Commun., 41, 2339 (1976)
Krumpolc M, Malek J, Makromol. Chem., 171, 69 (1973)
Mares F, Hetflezs J, Bazant V, Colln. Czech. Chem. Commun., 34, 3086 (1969)
Challa G, Rec. Trav. Chim., 79, 90 (1960)
Chang WL, Karalis T, J. Polym. Sci. A: Polym. Chem., 31, 493 (1993)
Tomita K, Ida H, Polymer, 14, 55 (1973)
Tomita K, Ida H, Polymer, 16, 185 (1975)
Flory PJ, Principles of Polymer Chemistry, Ch. III, p. 79, Cornell University Press, Ithaca. N.Y. (1953)
Shah TH, Bhatty JI, Gamlen GA, Dollimore D, Polymer, 25, 1333 (1984)

[1] Ravindranath K, Mashelkar RA, Chem. Eng. Sci., 41, 2197 (1986)

[2] Ravindranath K, Mashelkar RA, Chem. Eng. Sci., 41, 2969 (1986)

[3] Kotliar AM, J. Polym. Sci. Macromol. Rev., 16, 367 (1981)

[4] 양갑승, 최창남, 안계혁, 진성룡, 합성섬유의 고효율 중합(IV), p. 253, 과학기술처 (1991)

[5] Rod V, Diwani GE, Minarik M, Sir Z, Colln. Czech. Chem. Commun., 41, 2339 (1976)

[6] Krumpolc M, Malek J, Makromol. Chem., 171, 69 (1973)

[7] Mares F, Hetflezs J, Bazant V, Colln. Czech. Chem. Commun., 34, 3086 (1969)

[8] Challa G, Rec. Trav. Chim., 79, 90 (1960)

[9] Chang WL, Karalis T, J. Polym. Sci. A: Polym. Chem., 31, 493 (1993)

[10] Tomita K, Ida H, Polymer, 14, 55 (1973)

[11] Tomita K, Ida H, Polymer, 16, 185 (1975)

[12] Flory PJ, Principles of Polymer Chemistry, Ch. III, p. 79, Cornell University Press, Ithaca. N.Y. (1953)

[13] Shah TH, Bhatty JI, Gamlen GA, Dollimore D, Polymer, 25, 1333 (1984)