Korean Chemical Engineering Research

  • 제53권2호
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  • Pages.253-261
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  • 2015
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  • 0304-128X(pISSN)
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  • 2233-9558(eISSN)
한국화학공학회 (The Korean Institute of Chemical Engineers)
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Dimethyl terephthalate와 diethylene glycol의 에스테르 교환 반응

Transesterification of Dimethyl Terephthalate with Diethylene Glycol

  • Kim, Gunhyung (Department of Chemical Engineering, Chungnam National University) ;
  • Cho, Minjeong (Department of Chemical Engineering, Chungnam National University) ;
  • Jeon, Yeonghwan (Department of Chemical Engineering, Chungnam National University) ;
  • Han, Myungwan (Department of Chemical Engineering, Chungnam National University) ;
  • Kang, Kyungsuk (Siontech)
  • 투고 : 2014.07.19
  • 심사 : 2014.10.18
  • 발행 : 2015.04.01
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초록

DMT(dimethylterephthalate)와 DEG(diethylene glycol)의 에스테르 교환반응을 통하여 BHEET(bis-hydroxyethoxyethyl-terephthalate)을 생성하는 반응에 대하여 조사하였다. BHEET는 polyurethanr foam의 원료인 폴리에스터 폴리올의 단량체이다. DMT를 이용한 기존의 에스테르 교환 반응은 반응 중 생성 MeOH이 제거되는 반회분식 반응기를 사용하였다. 따라서 이러한 kinetics 연구에서는 역반응이 고려되지 않는다. 본 실험에서는 촉매로는 zinc acetate를 사용하였고, 소형 회분식 반응기를 통하여 DMT와 MeOH의 양을 정량하여 생성되는 MHEET와 BHEET를 추정하였다. 이 반응들에서 역반응을 고려한 보다 정확한 반응 kinetics를 조사하였다. 제안된 모델의 예측 값들이 실험값들과 잘 일치함을 보였다.

The kinetics of the transesterification of dimethyl terephthalate (DMT) with diethylene glycol (DEG) was studied in a batch reactor. bis-hydroxyethoxytethyl-terephthalate (BHEET), which is polyester polyol monomer, can be produced by the transesterification reaction. Zinc acetate was used as a catalyst. Previous kinetic studies was carried out in a semi-batch reactor where generated methanol was removed so that reverse reactions were not considered in the kinetic expressions, resulting in inaccuracy of the kinetic model. Mathematical models of a batch reactor for the tranesterification reaction, which took the reverse reaction into account, were developed and used to characterize the reaction kinetics and the composition distribution of the reaction products. More accurate models than previous ones were obtained and found to have a good agreement between model predictions and experimental data. Effect of process variables on the esterification reaction was investigated based on the experimental and simulation results.

키워드

참고문헌

  1. Singh, H., Sharma, T. P. and Jain, A. K., "Reactivity of the Raw Materials and Their Effects on the Structure and Properties of Rigid Polyurethane Foams," J. Appl. Polym. Sci., 106(2), 1014-1023(2007). https://doi.org/10.1002/app.26525
  2. Lee, Y. B., Choi, S. H., Choe, K. H., Seo, W. J., Whang, D. H. and Kim, W. N., "The Effect of the Polyols on Properties of Water Blown Rigid Polyurethane Foam," KIGAS., 5(6), 69-77(2002).
  3. Trovati, G., Sanches, E. A., Neto, S. C. and Mascarenhas, Y. P., "Characterization of Polyurethane Resins by FTIR, TGA, and XRD," J. Appl. Polym. Sci., 115(1) 263-268(2010). https://doi.org/10.1002/app.31096
  4. Szycher, M., "Szycher's Handbook of Polyurethanes," CRC press (1999).
  5. Choi, S. H., "Polyol for Polyurethane and Foam," Polym. Sci. Technol., 10(5) 621-628(1999).
  6. Han, M., "Development of Feedstock recycling Technology from Low-grade Polyester Wastes," R&D report of 21C Frontier Project (2006).
  7. Hubert, F., Durand, G. and Tersac, G., "Equilibria in the Alcoholysis Reactions of Terephthalic Esters and Chemical Valorization of Polyethyleneterephthalate Waste. I. Equilibrium Constants Determination," J. Appl. Polym. Sci., 72(3), 329-340(1999). https://doi.org/10.1002/(SICI)1097-4628(19990418)72:3<329::AID-APP3>3.0.CO;2-V
  8. Choi, K. Y., "A Modeling of Semibatch Reactors for Melt Transesterification of Dimethyl Terephthalate with Ethylene Glycol," Polym. Eng. Sci., 27(22), 1703-1712(1987). https://doi.org/10.1002/pen.760272210
  9. Besnoin, J. M., Lei, G. D. and Choi, K. Y., "Melt Transesterification of Dimethyl Terephthalate with Ethylene Glycol," AIChE J., 35(9), 1445-1456(1989). https://doi.org/10.1002/aic.690350905
  10. Santacesaria, E., Trulli, F., Minervini, L., Di Serio, M., Tesser, R. and Contessa, S., "Kinetic and Catalytic Aspects in Melt Transesterification of Dimethyl Terephthalate with Ethylene Glycol," J. Appl. Polym. Sci., 54(9), 1371-1384(1994). https://doi.org/10.1002/app.1994.070540919
  11. Di Serio, M., Tesser, R., Trulli, F. and Santacesaria, E., "Kinetic and Catalytic Aspects in Melt Transesterification of Dimethyl Terephthalate with Ethylene Glycol in the Presence of Different Catalytic Systems," J. Appl. Polym. Sci., 62(2), 409-415(1996). https://doi.org/10.1002/(SICI)1097-4628(19961010)62:2<409::AID-APP15>3.0.CO;2-W
  12. Tomita, K. and Ida, H., "Studies on the Formation of Poly(ethylene terephthalate): 2. Rate of Transesterification of Dimethyl Terephthalate with Ethylene Glycol," Polymer, 14(2), 55-60(1973). https://doi.org/10.1016/0032-3861(73)90096-7
  13. Hsu, J. and Choi, K. Y., "Kinetics of Transesterification of Dimethyl Terephthalate with 1,4-butanediol Catalyzed by Tetrabutyl Titanate," J. Appl. Polym. Sci., 32(1), 3117-3132(1986). https://doi.org/10.1002/app.1986.070320120
  14. Hsu, J. and Choi, K. Y., "Kinetics of Transesterification of Dimethyl Terephthalate with Poly(tetramethylene ether) Glycol and 1,4-butanediol Catalyzed by Tetrabutyl Titanate," J. Appl. Polym. Sci., 33(2), 329-351(1987). https://doi.org/10.1002/app.1987.070330206
  15. Yurramendi, L., Barandiaran, M. J. and Asua, J. M., "Kinetics of the Transesterification of Dimethyl Terephthalate with 1,4-butanediol," Polymer, 29(5), 871-874(1988). https://doi.org/10.1016/0032-3861(88)90146-2
  16. Lee, J., Cho, I., Jo, S., Cho, M., Han, M. and Kang, K., "Transesterification of Dimethyl Terephthalate with Ethylene Glycol," Korean Chem. Eng. Res., 51(1), 144-150(2013). https://doi.org/10.9713/kcer.2013.51.1.144
  17. Yong, L., Min, W., Li, G., Xiying, L. and Liqun, M., "Kinetics of Transesterification of Methyl Acetate and n-octanol Catalyzed by Cation Exchange Resins," Korean J. Chem. Eng., 30(5), 1039-1042 (2013). https://doi.org/10.1007/s11814-013-0023-x
  18. Barandiaran, M. J. and Asua, J. M., "Kinetic Analysis of the Transesterification of Dimethyl Terephthalate with Ethylene Glycol in a Semibatch Reactor," J. Polym. Sci. A Polym. Chem., 27(13), 4241-4255(1989). https://doi.org/10.1002/pola.1989.080271302
  19. Barandiaran, M. J. and Asua, J. M., "Analysis of Oligomerization in the Reaction of Dimethyl Terephthalate with Ethylene Glycol," Polymer, 31(7), 1352-1360(1990). https://doi.org/10.1016/0032-3861(90)90230-V