Novel High Nitrogen Insensitive Energetic Materials

Transcription

1 ovel High itrogen Insensitive Energetic Materials Presented at Workshop on Synthesis of Advanced Energetic Materials- The Path Forward Inn and Conference Center on the University of Maryland College Park campus April 3-5, 2011 By Farhad Forohar and Grissell Carrero-Martinez aval Surface Warfare Center, Indian Head, MD DISTRIBUTIO A. Approved for public release: distribution unlimited.

2 Objective The main objective is to develop energetic materials with high thermal stability and insensitivity to impact, friction, and electrostatic discharge. DISTRIBUTIO A. Approved for public release: distribution unlimited.

3 Background Looking into the chemical literature indicates that there is inherent thermal stability in some ring systems such as dibenzotetraazapentalene (TACOT) and dipicrylbenzobistriazoledione. O 2 O O 2 O 2 O 2 O 2 O O 2 Dipicrylbenzobistriazoledione mp = 430 C d = 1.80g/cc DISTRIBUTIO A. Approved for public release: distribution unlimited.

4 Compounds of Interest Triazole units fused into one ring system. Such a ring system has the advantage of being rich in nitrogen content, as well as having high thermal tolerance. R R R TT B Where R is: itroimidazole, H, O 2, itroalkyl, etc. DISTRIBUTIO A. Approved for public release: distribution unlimited.

5 Holden Calculations Holden calculation for some of the proposed molecules are listed below: R R Density(g/cc) O Trinitroimidazole 2.00 Dinitroimidazole 1.98 F 1.98 H 1.76 R R DISTRIBUTIO A. Approved for public release: distribution unlimited.

6 Literature Search A 1952 article in a Czech. publication describes synthesis of tris(alkyltriazolo)benzene ring system. (Muzik, F., et al., Org. Res Inst., Czech, 1952, 46, 774). A1993 Russian publication, by Samsonov et al., reports the synthesis of unsubstituted tris(triazolo)benzene. (Khimiya Geterotsiklicheskikh Soedinenii, o. 10., pp , October, 1993). DISTRIBUTIO A. Approved for public release: distribution unlimited.

7 Synthesis of Tris(triazolo)benzene H 2 H 2 O 2 H C l, a O 2 H 2 (O 2 )C 6 H 4 = = C 6 H 4 ( O 2 ) + H 2 H 2 H 2 H 2 = C 6 H 4 ( O 2 ) O 2 Pyridine C uso 4 O 2 C 6 H 4 ( O 2 ) (O 2 )C 6 H 4 H O 3 O 2 H 2 SO 4 O 2 C 6 H 4 ( O 2 ) M elting Point > 360 C 1) C H 3 O a in C H 3 O H 2) H C l O 2 H H H 2 O. M elting Point 300 C H (Sam sonov et al., K him iya G eterotsiklicheskikh Soedinenii, o. 10., pp , O ctober, 1993) DISTRIBUTIO A. Approved for public release: distribution unlimited.

8 Synthesis of Tris(nitrotriazolo)benzene, (TTB) H H H 2 O. (C H 3 C O ) 2 O + H O 3-5 o C H O 2 O 2 O 2 TTB DISTRIBUTIO A. Approved for public release: distribution unlimited.

9 13 C MR of TTB O 2 O 2 (in acetone, d6) O 2 DISTRIBUTIO A. Approved for public release: distribution unlimited.

10 IR of the Powder Form of TTB DISTRIBUTIO A. Approved for public release: distribution unlimited.

11 TTB Crystallization TTB crystallized out of acetone/water mixture. O 2 O 2 O 2 Or O 2 O 2 O 2 DISTRIBUTIO A. Approved for public release: distribution unlimited.

12 Picture of the Crystals DISTRIBUTIO A. Approved for public release: distribution unlimited.

13 X-ray Crystallography It shows the crystals are bis(2-nitrotriazolo)triazolobenzene. ote the two water molecules. By Dr. Damon Parrish at RL DISTRIBUTIO A. Approved for public release: distribution unlimited.

14 %T IR of Yellow Crystals Wavenumbers (cm-1) DISTRIBUTIO A. Approved for public release: distribution unlimited.

15 What Happened? During crystallization decomposition takes place. When the powder or the crystal is kept in a closed vial, after a few days at room temperature a strong acidic smell develops. The crystals are stable in the freezer. Crystallization in the absence of water may form more stable crystals. DISTRIBUTIO A. Approved for public release: distribution unlimited.

16 -Chlorination of TTB An Intermediate for Further Reactions H C l H B leach ( ao Cl) CH 3 C O O H C l H C l TTB TCTB TCTB was found to be a very interesting molecule. DISTRIBUTIO A. Approved for public release: distribution unlimited.

17 Mass Spectrum C l C l H C 6 H C l 3 9 m /e: (100.0% ) (95.9% ) (30.6% ) C l DISTRIBUTIO A. Approved for public release: distribution unlimited.

18 Heat of formation (calculated by Joe Hooper at SWCIHD to be 3900 kj/kg) is 3.8 times higher than that of CL-20. Holden calculation predicts a density of 1.94 g/cc. Stable under ambient conditions. Rapidly decomposes at 211 ºC. Preliminary tests show it is not impact or friction sensitive. It is a new oxidizer. Some Properties of TCTB It is hypergolic with PRIMARY LIQUID amines such as: aniline, hydrazine, diethylenetriamine and hydroxyethylethylenediamine. DISTRIBUTIO A. Approved for public release: distribution unlimited.

19 Hypergolic with Hydrazine DISTRIBUTIO A. Approved for public release: distribution unlimited.

20 Hypergolic with Hydrazine Cont d DISTRIBUTIO A. Approved for public release: distribution unlimited.

21 Hypergolic with Hydrazine Cont d DISTRIBUTIO A. Approved for public release: distribution unlimited.

22 Potential Applications An initiator. IRFA (Inhibited Red Fuming itric Acid) is used in rocket propulsion. IRFA is extremely corrosive. An oxidizing agent. A chlorinating agent. -chloramines are used for wastewater treatment, disinfectant in military kitchen services, and in dishwashing compositions. By analogy it should be a stronger reagent than the commercially available -chlorotriazolobenzene. DISTRIBUTIO A. Approved for public release: distribution unlimited.

23 1-Chlorobenzotriazole Has Commercial Uses DISTRIBUTIO A. Approved for public release: distribution unlimited.

24 1-Chlorobenzotriazole Has Many Applications M. P. Braun and C. R. Johnson, 1-Chlorobenzotriazole, in The Encyclopedia of Reagents, L. Paquette, Ed., John Wiley & Sons Limited, DISTRIBUTIO A. Approved for public release: distribution unlimited.

25 Compounds of Interest C l C ( O 2 ) 3 O 2 (O 2 ) 3 C O 2 C ( O 2 ) 3 DISTRIBUTIO A. Approved for public release: distribution unlimited.

26 Conclusions ovel nitro tristriazolobenzenes were made. One structure was confirmed by X-ray crystallography. Tris(chlorotriazolo)benzene was made. It has hypergolic properties. Tris(chlorotriazolo)benzene has potential commercial applications as an oxidant, a disinfectant and an energetic hypergolic agent! DISTRIBUTIO A. Approved for public release: distribution unlimited.

27 Acknowledgments The ILIR program for the funding. Alfred Stern Damon Parrish MID 1/C James Alan Friedlander Dorothy Cichra Jesse Moran Victor Bellitto Stanley Caulder Joseph A. Mackey DISTRIBUTIO A. Approved for public release: distribution unlimited.

28 IR Comparison Crystals Powder Wavenumbers (cm-1) DISTRIBUTIO A. Approved for public release: distribution unlimited.