Browse > Article

A Study Based on Molecular Orbital Theory of Polymerization of Oxetane High Explosives  

Kim, Joon-Tae (Department of Chemistry, Chosun University)
Publication Information
Applied Chemistry for Engineering / v.20, no.2, 2009 , pp. 159-164 More about this Journal
Abstract
Monomers of oxetane high explosives were theoretically examined in terms of reactivity, reaction mechanism and process of polymerization substituted by azido $(-CH_2N_3)$, nitrato $(-CH_2ONO_2)$ and hydrazino $(-CH_2N_2H_3)$ which belong to the 5th class hazardous materials and have explosiveness under acid catalyst using MINDO/3, MNDO, and AMI methods for formal charge, heat of formation, and energy level. Nucleophilicity and base of oxetane high explosives could be explained by negative charge size of oxetane oxygen atom and reactivity of oxetane in the growth stage of polymerization under acid catalyzer could be expected to be governed by positive charge size of axial carbon atom and low LUMO energy of electrophile. It could be estimated that carbenium ion was more beneficial in the conversion process of oxetane high explosives than that of stabilization energy (13.90~31.02 kcal/mole) of oxonium ion. In addition, concentration of oxonium ion and carbenium ion in equilibrium state influenced mechanism and it was also estimated that $S_N1$ mechanism reacts faster than that of $S_N2$ in prepolymer growth stage considering quick equilibrium based on form and calculation of polymerization under acid catalyzer.
Keywords
oxetane; high explosives; polymerization; oxonium ion; carbenium ion;
Citations & Related Records

Times Cited By SCOPUS : 1
연도 인용수 순위
1 G. E. Manser, R. W. Fletch, and G. C. Shaw, Report NR 84589, Office of Naval Research (1984)
2 J. C. W. Chien, Y. G. Cheun, and C. P. Lilya, Marcromolecules, 3, 870 (1988)
3 Y. G. Cheun, J. Kor. Chem. Soc., 35, 461 (1991)
4 G. E. Manser, Technology of Polymer Compounds and Energetic Materials, Mcgraw-Hill Book Company, 50 (1990)
5 M. J. S. Dewar, E. G. Healy, and J. J. P. Stewart, QCPE, Program 506, Version 2.10 was used in this work
6 M. J. S. Dewar, E. G. Zoebisch, and J. J. P. Stewart, J. Am. Chem. Soc., 107, 3902 (1985)   DOI
7 B. Xu, C. P. Lilly, and J. C. W. Chien, Macromolecules., 20, 1445 (1987)   DOI
8 G. Klopman, J. Am. Chem. Soc., 90, 225 (1986)
9 R. L. Willer and R. S. Day, Reprint 258 (1989)
10 C. Liang and L. C. Allen, J. Am. Chem. Soc., 113, 1878 (1991)   DOI
11 I. Fleming, Frontier Orbitals and Organic Chemical Reactions, Wiley Interscience, New York (2006)
12 S. Penczek, P. Kubisa, and R. Szymanski, Makromol. Chem., Macromol, Symp., 3, 203 (1986)   DOI
13 D. Cremer and E. Eraka, J. Am. Chem. Soc., 107, 3800 (1985)   DOI
14 E. J. Corey and N. Raju, Tetrahedron Letters, 24, 5571 (1983)   DOI   ScienceOn
15 E. L Eliel and K. M. Pietrusiewicz, Top Carbon-13 NMR spectroscopy, 3, 172, New York (1979)