Optimization and Elucidation of Esterification between Adipic Acid and 1,4-Butane Diol

Adipic acid와 1,4-butane diol의 에스테르화 반응 최적화 및 반응기작 규명

  • Published : 2003.06.01

Abstract

Aliphatic polyester, especially poly(butylene adipate)(PBA), is quite biodegradable and one of the most promising polymer materials to be commercialized. Bis(4-hydroxybutyl) adipate (BHBA) formation stage is the first principal process in the production of PBA from adipic acid (AA) and 1,4-butane diol (BD). In this study, we investigated for the effective production of Bis(4-hydroxybutyl) adipate (BHBA), effects of molar ratio of adipic acid (AA) to 1,4-butane diol (BD), catalyst (tetrabutyl titanate, TBT) concentration, and temperature on the reaction rate of esterification between AA and BD were investigated. Initial reaction rate of the esterification decreased with increasing molar ratio of AA to BD and reaction temperature, whereas reaction constant increased with increase in catalyst-concentration. Activation energy values for catalyzed and uncatalyzed esterifications were 198.5 and 94.8 kJ/mol, respectively.

Keywords

esterification;catalyst;temperature dependence

References

  1. Tokiwa, Y. and Suzuki, T. Hydrolysis of copolyesters containing aromatic and aliphatic ester blocks by lipase. J. Appl. Polym. Sci, 26: 441-448 (1981) https://doi.org/10.1002/app.1981.070260206
  2. Shah, T.H., Bhatty, J.I. and Gamlen, G.A. Aspects of the chemistry of poly(ethylene terephthalate). III. Transesterification of dimethylterephthalate with ethylene glycol in the presence of various catalytic systems. J. Macromol. Sci. 4: 431-443 (1984)
  3. Flory, P.J. Principles of Polymer Chemistry, 3rd ed., pp. 69-104. Cornell University Press, New York, USA (1953)
  4. Datye, K.V. and Raje, H.M. Kinetics of transesterification of dimethyl terephthalate with ethylene glycol. J. Appl. Polym. Sci. 30: 205-219 (1985) https://doi.org/10.1002/app.1985.070300117
  5. Park, S.S., Jun, H.W. and Im, S.S. Kinetics of forming poly(butylene succinate) (PBS) oligomer in the presence of MBTO catalyst. Polym. Eng. Sci. 38: 905-914 (1998) https://doi.org/10.1002/pen.10257
  6. Levenspiel, O. Chemical Reaction Engineering, 2nd ed., pp. 8-40. John Wiley & Sons, Inc., New York, USA (1972)
  7. Tomita, K. and Ida, H. Studies on the formation of poly(ethylene terephthalate): 3. Catalytic activity of metal compounds in transesterification of dimethyl terephthalate with ethylene glycol. Polymer 16: 185-190 (1975) https://doi.org/10.1016/0032-3861(75)90051-8
  8. Walker, C.C. The inhibitory effect of carboxylic acids on the catalyzed reaction between dimethyl terephthalate and ethylene glycol. J. Polym. Sci. 21: 623-626 (1983)
  9. Hovenkamp, S.G. Kinetic aspects of catalyzed reactions in the formation of poly(ethylene terephthalate). J. Polym. Sci. 9: 3617-3625 (1971)
  10. Hoeschele, G.K. Process for preparing polyesters using a catalyst mixture of tetra-alkyl titanates and zirconates. EP Patent 0,472,179 A2 (1991)
  11. Otton, J., Ratton, S., Vasney, V.A., Markova, G.D., Nametov, K.M., Bakhmutov, V.I., Vinogradova, S.V. and Korshak, V.V. Investigation of the formation of poly(ethylene terephthalate) with model molecules. III. Metal- catalyzed esterification and alcoholysis reactions: Influence of the structure of the reactants and of the nature of the reaction medium. J. Polym. Sci. 27: 3535-3550 (1989)
  12. Chang, W.L and Karalis, T. Polyesterification reactions of adipic acid-based polyesters. J. Polym. Sci. 31: 493-504 (1993)