NWC TP 7073 Explosive Properties of Polynitroaromatics by NWilliam S. Wilson %, Dan E. Bliss Stephen L. Christian I D and David J. Knight Research Department APRIL 1990 NAVAL WEAPONS CENTER ELECTE CHINA LAKE, CA 93555-6001 A DEC 1 U Approved for public release; distribution is unlimited. Naval Weapons Center FOREWORD (U) A large number of polynitroaromatic compounds have been prepared at the Naval Weapons Center in programs directed toward the synthesis of new dense, powerful, and insensitive energetic materials. This report collates their explosive properties, including density, detonation velocity and pressure, and impact sensitivity, and attempts to identify structure/property correlations. Such correlations will provide greater understanding of energetic materials in general and should a!!ow the rational, scientific identification of desirable target materials for new synthetic programs. This work was carried out using funding from the Naval Surface Warfare Center, Silver Spring, Md., Program Element 62314N, Project Number 2107F, Task Area RJ14E31, and Work Unit 132120 under the sponsorhip of L. Roslund (R10C). This report has been reviewed for technical accuracy by John W. Fischer, Richard A. Hollins, and Arnold T. Nielsen. Approved by Under authority of R. L. DERR, Head D.W. COOK Research Department Capt., USN 27 April 1990 Commander Released for publicalion by WILUAM PORTER Technical Director NWC Technical Publication 7073 Published by ...................................................... Technical Information Department Collation ........................................................................................ 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TFTLE AND SUBTITLE 5 FUNDING NUMBERS Explosive Properties of Polynitroaromatics (U) PE 62314N PN 2107F L AUHMS)TA RJ14E31 Wilia S.Wilson, Dan E. Bliss, Stephen L. Christian, WU 132120 and David J. Knight 7. PERFORMINGORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION REPORT NUMBER Naval Weapons Center China Lake, CA 93555-6001 NWC TP 7073 S.SPONSORNGIMOOMTORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSONGMOMTOMfNG AGENCY REPORT NUMBER Naval Surface Warfare Center Silver Spring, MD 11. SUPPLEETARY NOTES 12&. OISMTI ONIAVAILANUTY STATEMENT i2b. CISTEBUION CODE Approved for public release; distribution is unlimited. 13. ABSTRACT (Afaxsnn 200l words) (U) A large number of polynitroaromatic compounds have been prepared in these laboratories over the last decade or so during programs to develop new energetic materials. This report documents their explosive properties, including density, detonation velocity and pressure, and impact sensitivity, -and attempts to rationalize trends in those properties in terms of structure/property correlations. 14. SUBJECT TERMIS iS. NMBER OF PAGES Density, Detonation Pressure, Detonation Velocity, Explosives, 3 0 Impact Sensitivity, Polynitroaromatics, Structure/Property Correlations it PRICE COD 17. SECUSTY C3SSAW ZI I ii SECUF.TY CLASSIFICATION i. SECUnTY CLASSIFCAIMO K. UMIATION OF ASTRACT UNCLASSIFIED UNCLASSIFIED UNCLASSIFIED NOWE NSN 7540-01-280-5500 SWad Form 298 (Rev. 2-09) P cbbANSIStU2Sg18A NWC TP 7073 CONTENTS Introduction ............................................................................................................... 3 Results and Discussion ............................................................................................... 3 Velocities of Detonation ................................................................................... 6 Densities ......................................................................................................... 7 Impact Sensitivies .......................................................................................... 9 Conclusions ............................................................................................................... 1 8 References ............................................................................................................. 2 0 Appendix: Structures of Polynitroaromatic Compounds Studied ............................. 25 AqoesslO e r ' TIS 4A&I DTIC TAR 0l Unannounced 0 Ju6tificatton By Distribution./ Codes AvailabilitytAvaj ld dor Dist SPcial NWC TP 7073 INTRODUCTION A concentrated effort over the past decade or so has been devoted to the synthesis of new energetic materials in these laboratories. Th3 aims of this synthetic effort have been the development of denser, more powerful explosive and propellant ingredients and the identification of less sensitive and, therefore, safer materials without sacrifice of current standards of performance. This synthetic program has been focussed largely on new cyclic (Reference 1) and more recently caged nitramines (Reference 2) (which will not be considered here), and on highly substituted polynitroaromatic compounds (Reference 3). Undoubtedly, the highlight of this latter work was the successful synthesis of hexanitrobenzene (HNB). The stratagem employed, namely nitration of a suitably substituted nitroaniline followed by the novel oxidation of the amine function- ality using peroxydisulfuric acid, has proven useful in the synthesis of a whole range of polynitroaromatics. Another class of compounds, the nitrated and aminated benzo- furoxans, has provided an equally fertiie source of new energetic and insensitive ingredients (Reference 4). The syntheses of these polynitroaromatic energetic materials and related benzo- furoxans have been reported in a number of documents, including both Naval Weapons Center (NWC) technical reports and scientific journals. Therefore, these procedures will not be reproduced here. On the other hand, the explosive properties measured and/or calculated for these compounds, such as density, velocity and pressure of detonation, and particularly impact sensitivity, have been largely unreported. This report documents these properties for the series of such polynitro-aromatics and benzofuroxans prepared at NWC and attempts to rationalize them and identify underlying structure/property correlations. An understanding of such structure/property relationships is essential for the systematic, scientific formulation of appropriate targets for synthesis as potential new energetic materials. RESULTS AND DISCUSSION The compounds considered in this report are listed in Table 1, together with their entry numbers, acronyms, and chemical formulae. The structural formulae are given in the Apnendix. 3 NWC TP 7073 TABLE 1. Polynitroaromatic Compounds Studied. No. Acronym Chemical name Formula I HNtB Hexanitrobenzene C6N60 12 2 PNB Pentanitrobenzene C6HN5010 3 TetNB3 1,2,3,5-Tetranitrobenzene CAJ4N0c 4 TNB 1,3,5-Trinitrobenzene C6H3NAc 5 Picric acid 2,4,6-Trinitrophenol C%0 6 PNA Pentanitroaniline C*H2N6010 7 TetNA 2,3,4,6-Tetranitroaniline C&H-AN5 8 TNA 2,4,6-Trinitroaniline C"1-s406 9 DATB 1 ,3-Diamino-2,4,6-trinitrobenzene CAJtNAc 1 0 TATB 1,3,5-Triarnino-2,4,6-trinitrobenzene C"JIN 6 1 1 ItJBP 2,2',4,4',6,6'-Hexanitrobiphenyl C12H4N6012 1 2 DRPAM 3,3'-D jam ino-2,2', 4,4',6,6'-hexan itrobiphe nyl CIANS012 1 3 CL-i12 4,4'-Diamino-2,2',3,3',5,5',6,6'-octanitrobiphenyI C12H4N10016 1 4 IDNBP 2,2',3,3',4,4',5,5.,6,6'-DecanitrobiphenyI C12N, 00O0 1 5 DN8F 4,6-Dinitrobenzofuroxan C6H2N06 1 6 ADNBF 7-Amino-4,6-dinitrobenzofuroxan C6I-IN 5c4 1 7 CL- 14 5,7-Diamino-4,6-dinitrobenzofuroxan C"HN 6 1 a CL-17 7-Amino-4,5,6-trinitrobenzofuroxan CdviANO 1 9 CL-18 8-Amino-7-nitrobenzobisfuroxan CN4A 2 0 BTF Benzotrifuroxan CA-or. 2 1 PNT Pentanitrotoluene CAHN 50, 0 2 2 2,3,4,5-TetNT 2,3,4,5-Tetranitrotoluene C7H4NAc 2 3 2,3,4,6-TetNT 2,3,4,6-Tetranitrotoluene CAHN 408 2 4 2,3,5,6-TetNT 2,3,5,6-Tetranitrotoluene 07H4N4OR 2 5 2,4,6-TNT 2,4,6-Trmnitrotoluene C~A5N06 2 6 2,3,4-TNT 2,3,4-Trinitrotoluene C7445N0c 2 7 3,4,5-TNT 3,4,5-Trinitrotoluene C7l-IsNrc 2 8 TetN-o-ToI 2-Amino-3,4,5,6 -tetranitrotoluene CAHN 5O4 2 9 TetN-m-ToI 3-Amino-2,4,5,6-tetranitrotoluene C71 5 c 3 0 TetN-p-ToI 4-Amino-2,3,5, -tetranitrotoluene C7H5N5 3 1 HNDPM 2,2',4,4',6,6' -Hexanitrodiphenylmethane C13H6N6012 3 2 Picryl azide 2-Azido-1 ,3,5-trinitrobenzene CSH-2N5(4 3 3 CL-i16 Azidopentanitrobenzene Cr6N8010 3 4 DONP 2-Diazo-4,6-dinitrophenol %H2N0 3 5 5-CI-DDNP 5-Chloro-2-diazo-4,6-dinitrophenoI C6HN4O5a 3 6 W1N0 2-DDNP 3-Methyl-2-diazo-4,5,6-trinitrophenol C7I-INsc 3 7 Trntryl N-Methyl- N,2A ,6-tel, anitroaniline C7H5N,(f* 3 8 (MeNO2N)-22 N-Methyl-2-armerio-N4,3,4,5,6-pentanitrotoluene C81-H16 6O 3 9 (MeNO2N)-23 N-Methyl-3-amino-N,2,4,5,6-pentanitrotoluene C811N601 4 NWC TP 7073 Table 2 lists the various explosive properties determined for these polynitro- aromatics, including predicted velocity of detonation and detonation pressure, calculated