헤테로폴리산 촉매를 이용한 Tetrahydrodicyclopentadiene 및 Tetrahydrodi(methylcyclopentadiene)의 이성화반응 연구

정병훈; 한정식; 김성보; 강철한; 이범재; Byung Hun Jeong; Jeong Sik Han; Seong Bo Kim; Cheol Han Kang; Bum Jae Lee

Journal of the Korean Industrial and Engineering Chemistry, Vol.18, No.1, 36-40, February, 2007

Study on the Isomerization Reaction of Tetrahydrodicyclopentadiene, Tetrahydrodi(methylcyclopentadiene) Using Heteropolyacid Catalyst

정병훈^†, 한정식, 김성보 ¹, 강철한², 이범재 ²

국방과학연구소
¹한국화학연구원 화학기술부
²충남대학교 정밀공업화학과

Byung Hun Jeong^†, Jeong Sik Han, Seong Bo Kim¹, Cheol Han Kang², and Bum Jae Lee²

Agency for Defense Development, Yuseong C.P.O Box 35-5, Daejon 305-152, Korea
¹Advanced Chemical Technology Division, Korea Research Institute of Chemical Technology, Daejon 305-600, Korea
²Department of Fine Chemical Engineering, Chung Nam National University, Gung-dong Yuseong-gu, Daejon 305-764, Korea

E-mail:

초록

헤테로폴리산 촉매를 이용하여 endo-tetrahydrodicyclopentadiene 및 endo-tetrahydrodi(methylcyclopentadiene)의 이성화반응에 관한 연구를 행하였다. 이성화반응에 의해 endo 형태를 exo 형태의 화합물로 제조하였다. 기존의 이성화촉매인 알루미늄 클로라이드의 문제점을 개선하기 위하여 헤테로폴리산의 적용을 시도하였다. Keggin 형태의 헤테로폴리산 촉매인 H3PW12O40에서 수소원자 2.5개 대신에 cesium으로 치환시 촉매활성이 가장 높았다. Cesium으로 치환된 헤테로폴리산 촉매 사용시 기존의 알루미늄클로라이드 촉매보다 이성화반응속도가 빠른 것을 확인하였고, 반응온도, 시간에 따른 tetrahydrodicyclopentadiene 및 tetrahydrodi(methylcyclopentadiene)의 반응성을 비교하였다.

The study on the isomerization reaction of endo-tetrahydrodicyclopentadiene and endo-tetrahydrodi(methylcyclopentadiene) using heteropolyacid catalyst was carried out. Exo compound was prepared from endo compound through isomerization reaction. To improve the problem of aluminum chloride as an isomerization catalyst, application of heteropolyacid was attempted. In use of Keggin type heteropolyacid, catalytic activity was extremely high at cesium substitution instead of 2.5 hydrogen atoms of H3PW12O40. Using the cesium substituted heteropolyacid, isomerization reaction rate was faster than aluminum chloride and the effect of reaction temperature and times on reactivities were compared in isomerization of tetrahydrodicyclopentadiene and tetrahydrodi(methylcyclopentadiene).

Keywords:tetrahydrodicyclopentadiene;tetrahydrodi(methylcyclopentadiene);isomerization;heteropolyacid;cesium salt

[References]

Eijkman JF, Chem. Week, 1, 7 (1903)
Eijkman JF, Chem. Week, 3, 685 (1906)
Mark H, Mcketta F, Pthmer DJ, Kirkothmer Encyclopedia of Chemical Technology, 132, Jone Wiley & Sons, Inc., Newyork (1968)
Skala D, Hanika J, Pet. Coal, 45, 105 (2003)
Jeong BH, Han JS, Lee JH, Kim SB, Lee BJ, Chem. Eng. Res., 43, 566 (2005)
Xing E, Mi Z, Xin C, Wang L, Zhang X, J. Mol. Catal. A-Chem., 231, 161 (2005)
Schleyer PVR, Donaldson MM, J. Am. Ceram. Soc., 82, 4645 (1960)
Du YM, Li CY, Lu J, Chinese J. Explos. Propel., 28, 58 (2005)
Okuhara T, Nishimura T, Misono M, Stud. Surf. Sci. Catal., 101, 581 (1996)
Okuhara T, Watanabe H, Nishimura T, Inumaru K, Misono M, Chem. Mater., 12, 2230 (2000)
Misono M, Catal. Rev., 29, 269 (1987)
Essayem N, Tong YY, Jobic H, Vedrine JC, Appl. Catal. A: Gen., 194, 102 (2000)
Xing E, Zhang X, Wang L, Mi Z, Catal. Commun., 6, 737 (2005)

[Referenced By]

[Related Articles]

[1] Eijkman JF, Chem. Week, 1, 7 (1903)

[2] Eijkman JF, Chem. Week, 3, 685 (1906)

[3] Mark H, Mcketta F, Pthmer DJ, Kirkothmer Encyclopedia of Chemical Technology, 132, Jone Wiley & Sons, Inc., Newyork (1968)

[4] Skala D, Hanika J, Pet. Coal, 45, 105 (2003)

[5] Jeong BH, Han JS, Lee JH, Kim SB, Lee BJ, Chem. Eng. Res., 43, 566 (2005)

[6] Xing E, Mi Z, Xin C, Wang L, Zhang X, J. Mol. Catal. A-Chem., 231, 161 (2005)

[7] Schleyer PVR, Donaldson MM, J. Am. Ceram. Soc., 82, 4645 (1960)

[8] Du YM, Li CY, Lu J, Chinese J. Explos. Propel., 28, 58 (2005)

[9] Okuhara T, Nishimura T, Misono M, Stud. Surf. Sci. Catal., 101, 581 (1996)

[10] Okuhara T, Watanabe H, Nishimura T, Inumaru K, Misono M, Chem. Mater., 12, 2230 (2000)

[11] Misono M, Catal. Rev., 29, 269 (1987)

[12] Essayem N, Tong YY, Jobic H, Vedrine JC, Appl. Catal. A: Gen., 194, 102 (2000)

[13] Xing E, Zhang X, Wang L, Mi Z, Catal. Commun., 6, 737 (2005)