Study on the Hydrogenation and Isomerization Reaction of Dimethylcyclopentadiene

디메틸시클로펜타디엔의 수소화 및 이성화반응 연구

  • Jeong, Byung Hun (Agency for Defense Development) ;
  • Han, Jeong Sik (Agency for Defense Development) ;
  • Lee, Jeong Ho (Advanced Chemical Technology Division, Korea Research Institute of Chemical Technology) ;
  • Kim, Seong Bo (Advanced Chemical Technology Division, Korea Research Institute of Chemical Technology) ;
  • Lee, Bum Jae (Department of Fine Chemical Engineering, ChungNam National University)
  • Received : 2005.07.25
  • Accepted : 2005.09.22
  • Published : 2005.10.31

Abstract

The study on the hydrogenation and isomerization of unsaturated bicyclic hydrcarbon compounds using methylcyclopentadiene dimer (MCPD) was carried out. Exo compound was prepared through isomerization reaction after two hydrogenation reaction steps. In the first hydrogenation reaction which needs one mole of hydrogen, the formation rate of monomer was increased as dimer was decomposed at reaction temperature above $100^{\circ}C$. At first hydrogenation, DHDMCPD [dihydrodi(methylcyclopentadiene)] was formed and second hydrogenation was proceeded to produce THDMCPD [tetrahydrodi(methylcyclopentadiene)], the ratio of exo to endo THDMCPD was varied by the control of 2nd hydrogenation temperature. To improve the process, continuous 1st and 2nd hydrogenation conditions were established by using the 2nd stage heat controllable reactor. Also, catalytic activities were compared by the use of halogenized aluminum, metal halides and solid acids catalysts on the isomerization reaction from endo to exo THDMCPD.

이중고리형 불포화탄화수소 화합물인 methylcyclopentadiene dimer(MCPD)의 수소화 및 이성화반응에 관한 연구를 행하였다. Exo 화합물은 2단계의 수소화반응 후에 이성화반응에 의해 제조되었다. 수소 1몰이 첨가되는 1차 수소화 반응은 $100^{\circ}C$이상의 반응온도에서는 다이머가 분해되어 모노머가 생성이 증가되었다. 1차 수소화 반응에 의하여 DHDMCPD[dihydrodi(methylcyclopentadiene)]가 생성된 후 2차 수소화반응을 진행하여 THDMCPD[tetrahydrodi (methylcyclopentadiene)]를 제조하였는데, 2차 반응온도조절에 의해 exo와 endo 비율이 변화되었다. 공정개선을 위하여 2단 가열반응기를 사용함으로 연속식 1, 2차 수소화 조건을 확립하였고 또한 endo THDMCPD로부터 exo 형태로 의 이성화반응에 할로겐화 알루미늄과 같은 할로겐화 금속촉매와 고체산 촉매를 사용하여 촉매의 활성을 비교하였다.

Keywords

References

  1. Alder, K. and Sein, G., 'Polymerization of Cyclic Hydrocarbons, VII. The Energy Content of Polymeric Cyclopentadienes, a Contribution to the Strain Theory,' Ber., 67B, 613-634(1934)
  2. Pirsch, J., 'Solvents for Organic,' Ber., 67B, 1115-1142(1934)
  3. Mark, H. F., McKetta, A. and Pthmer, D. J., Kirkothmer Encyclopedia of Chemical Technology, Jone Wiley & Sons, Inc., Newyork (1968)
  4. Armengol, E., Corma, A., Garcia, H. and Primo, J., 'Acid Zeolites As Catalysts in Organic Reactions, Tert-Butylation of Anthracene, Naphthalene and Thianthrene,' A, Primo, J., 149(2), 411-423(1997)
  5. Miller, J. M., Goodchild, M., Lakshmi, J. l., Wails, D. and Hartman, J. S., 'Friedel-Crafts Catalysis Using Supported Reagents, Synthesis, Characterization and Catalytic Application of ZnCl2 Supported on Fluoride-Modified Sol-gel Derived Aluminosilicates,' J. S., Catal. Lett., 63(3/4), 199-204(1999) https://doi.org/10.1023/A:1019045811205
  6. Jun, S. and Ryoo, R., 'Aluminum Impregnation Into Mesoporous Silica Molecular Sieves for Catalytic Application to Fridel- Crafts Alkylation,' J. Catal., 195(2), 237-243(2000) https://doi.org/10.1006/jcat.2000.2999
  7. Izumi, Y., Onaka, M. and Urabe, K., 'Alkali Metal Salts and Ammonium Salts of Keggin-Type Heteropolyacids as Solid Catalysts for Liquid-Phase Friedel-Crafts Reactions,' Appl. Catal. A, 132(1), 127-140(1995) https://doi.org/10.1016/0926-860X(95)00167-0
  8. Quasching, V., Deutch, J., Druska, P., Niclas, H. J. and Kemnitz, E., 'Properties of Modified Zirconia Used as Friedel-Crafts-Acylation Catalysts,' J. Catal., 177(2), 164-174(1998) https://doi.org/10.1006/jcat.1998.2098
  9. Heidekum, A., Hamm, M. A. and Hoelderich, F., 'Nafion/Silica Composite Material Reveals High Catalytic Potential in Acylation Reactions,' J. Catal., 188(1), 230-232(1999) https://doi.org/10.1006/jcat.1999.2656
  10. Janoski, E. J., Schneider, A. and Ware, R. E., 'Process for Isomerization of Tetrahydrodicyclopentadiene,' U.S. Patent No. 4,288,644 (1981)