Journal of Integrative Natural Science (통합자연과학논문집)

The Basic Science Institute Chosun University (조선대학교 기초과학연구원)
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Theoretical Study on Polymerization of Oxepane High Explosives

  • Received : 2012.07.19
  • Accepted : 2012.09.25
  • Published : 2012.09.30
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Abstract

Oxepane high explosives substituted to explosive group such as azido, nitrato and hydrazino are investigated theoretically the acid catalyzed reaction using the semiempirical MINDO/3, MNDO and AM1 methods to use as the guidelines of high explosives. The nucleophilicity and basicity of oxepane high explosives can be explained by the value of negative charge on oxygen atom of oxepane and the reactivity in propagation step can be represented by the value of positive charge on carbon atom and low electrophile LUMO energy. It was known that carbenium ion was favorable due to the stable energy (19.507~32.101 Kcal/mol) between oxonium ion and carbenium ion in the process of cyclic oxonium ion of oxepane high explosives being converted to open carbenium ion in oxepane high explosives. The value of concentration of cyclic oxonium ion and open carbenium ion in equilibrium status was found to be a major determinant of mechanism, it was expected to react faster in the prepolymer propagation step in SN1 mechanism than in that of $S_N2$.

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References

  1. S. Penczek, P. Kubisa, and R. Szymmanski, "Activated monomer propagation in cationic polymerizations", Makromol. Chem., Macromol. Symp. Vol. 3, pp. 203-220, 1986.
  2. P. M. Lahti and C. P. Lillya, "An AM1 computational study of the cationic polymerization mechanism of cyclic acetals", Macromolecules, Vol. 23, pp. 1214-1218, 1990. https://doi.org/10.1021/ma00206a048
  3. D. Cremer and E. Kraka, "Theoretical determination of molecular structure and conformation. 15. Threemembered rings: bent bond, ring strain, and surface delocalization", J. Am. Chem. Soc., Vol. 107, pp. 3800-3810, 1985. https://doi.org/10.1021/ja00299a009
  4. S. Penczek and R. Szymanski, "The carbenium iononium ion equilibria in cationic polymerization", Polym. J., Vol. 12, pp. 617-628, 1980. https://doi.org/10.1295/polymj.12.617
  5. J. C. W. Chien, Y. G. Cheun, and C. P. Lilya, "Cationic polymerization of dioxepane and its 2-alkyl derivatives", Macromolecules, Vol. 21, pp. 870-875, 1988. https://doi.org/10.1021/ma00182a003
  6. S. Sasaki, "Handbook of proton-NMR spectra and data", Asahi Research Center Co. Ltd (Ed), Academic Press Inc., Tokyo, Vol. 1-5 ,1985.
  7. Y. G. Cheun, J. T. Kim, and S. K. Park, "Theoretical studies on the cationic polymerization mechanism of oxetanes", J. Korean Chem. Soc., Vol. 35, pp. 636-644, 1991.
  8. J. T. Kim, "A study based on molecular orbital theory polymerization of oxetane high explosives", J. Korean Ind. Eng. Chem., Vol. 20, pp. 159-164, 2009.
  9. N. P. Cheremisinoff (Ed). "Handbook of polymer science and technology", Marcel Dekker, Inc., New York and Basel, Vol. 3, PP. 503-539, 1989.
  10. S. C. Moon, H. S. Jung, J. C. Lee, J. W. Hong, J. K. Choi, and B. W. Jo, "Preparation and properties of low density polyethylene/organo claynano composite", J. Korean Ind. Eng. Chem., Vol. 16, pp. 52- 60, 2005.
  11. S. H. Park, T. V. Phuong, H. W. Song, K. N. Park, B. M. Kim, and Y. S. Choe, "Mechanical properties and morphology of epoxy/polyamide/DDS/2E4MZCNS reactive blends", J. Korean Ind. Eng. Chem., Vol. 19, pp. 471-476, 2008.
  12. M. J. S. Dewar, E. G. Healy, and J. J. P. Stewart, QCPE, Program 506, Version 2.10 was used in this work.
  13. M. J. S. Dewar, E. G. Zoebisch, and J. J. P. Stewart, "Development and use of quantum mechanical molecular models. 76. AM1: A new general purpose quantum mechanical molecular model", J. Am. Chem. Soc., Vol. 107, pp. 3902-3909, 1985. https://doi.org/10.1021/ja00299a024
  14. I. Fleming, "Frontier orbitals and organic chemical reactions", 5th Eds., Wiley Interscience, New York, 2006.
  15. G. Klopman, "Chemical reactivity and the concept of charge and frontier controlled reactions", J. Am. Chem. Soc., Vol. 90, pp. 223-225, 1968. https://doi.org/10.1021/ja01004a002
  16. B. Bigot, A. Sevin, and A. Devaquet, "Ab initio SCF calculation on the photochemical behavior of the three-membered rings, 3. Oxirane: ring opening" J. Am. Chem. Soc., Vol. 101, pp. 1095-1100, 1979. https://doi.org/10.1021/ja00499a007

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