A Low Sensitivity Energetic Salt Based on Furazan Derivative and

Article pubs.acs.org/jced

A Low Sensitivity Energetic Salt Based on Furazan Derivative and Melamine: Synthesis, Structure, Density Functional Theory Calculation, and Physicochemical Property Xin Li,† Xiangyu Liu,†,§ Sheng Zhang,† Haipeng Wu,† Bozhou Wang,‡ Qi Yang,† Qing Wei,† Gang Xie,† Sanping Chen,*,† and Shengli Gao† †

Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an, Shaanxi 710069, People’s Republic of China ‡ Xi’an Modern Chemistry Research Institute, Xi’an 710065, China § School of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, China S Supporting Information *

ABSTRACT: Reaction of 4,4′-oxybis[3,3′-(1H-5-tetrazol)]furazan (H2BTFOF, 1) with melamine (MA) leads to a energetic salt (MA+)·(HBTFOF¯)·H2O (2). The structure of 2 was characterized by single-crystal X-ray analysis. Thermogravimetry analysis indicates that the main framework of 2 possesses good thermal stability up to 501 K. Optimized structure, total energy and the frontier orbital energy of 2 were investigated in detail. As to the thermodecomposition reaction of the main framework for 2, the nonisothermal thermokinetics parameters were obtained by Kissinger’s and Ozawa’s methods. The standard molar enthalpy of formation of 2 was calculated as being (518.55 ± 6.30) kJ·mol−1 from the constantvolume combustion energy determined by a rotating-bomb microcalorimeter. Importantly, 2 has a very low sensitivity to friction (>360 N) and impact (38 J), which makes it of interest in new environmentally friendly, insensitive energetic materials.

1. INTRODUTION Traditional energetic materials, such as cyclo-1,3,5-trimethylene-2,4,6-trinitamine (RDX), 1,2 2,4,6-trinitrotoluene (TNT), 3 − 5 and 1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX),6−8 have been used for a variety of military purposes and civilian applications.9−11 Many catastrophic explosions of these compounds12 urge researchers to synthesize new energetic materials with higher safety as well as good performance. As the desirable requirements, the modern explosives and propellants should possess good thermal stability, impact and shock insensitivity, and other better performance.12 As known, ionic energetic salts could benefit for formation of strong hydrogen-bonding networks and π−π stacking interactions to show remarkable thermal stability, considerable insensitivity to physical stimulus, and explosive performance, which has attracted considerable interest.13−16 T. M. Klapötke and J. M. Shreeve groups have reported many ionic energetic materials, such as bis[3-(5-nitroimino-1,2,4-triazolate)]-based,17 5,5′-bis(tetrazole)-based,18 nitraminofurazane-based,19 and bis(1-oxidotetrazolyl)furazane-based20 energetic salts. Among these compounds, furazan group can markedly improve the performance of explosives due to its high density, high positive heat of formation, and good oxygen balance.21 However, furazan ring is limited to form an anion in energetic salts because of the absence of an acidic proton,22 making it © 2015 American Chemical Society

impossible to serve as a BrØsted acid or to pair with a Lewis base. Nonetheless, the assembly of furazan with other energetic backbones containing acidic protons in a molecule may be beneficial to generate new energetic salts with better performance. Naturally thinking, the compounds of tetrazole ring conjugated with furazan not only produce acidic hydrogen to show deprotonated characteristic but also can remarkable improve detonation property because of their high nitrogen content and high positive heat of formation.21,23 Consequently, a furazan derivative, 4,4′-oxybis[3,3′-(1H-5tetrazol)]furazan (H2BTFOF), is our first choice to construct energetic salt, based on the following reasons: (1) The compound fulfills an important role in improving the performance of explosives because of its high nitrogen content (N% = 57.90), high density (ρ = 1.74 g·cm−3), good oxygen balance (Ω% = −55.14), and high thermal degradation (Td = 513 K).21,23 (2) What’s more, the furazan rings conjugated with two tetrazoles is propitious to form anions for constructing energetic salts. For the choice of a cation, the melamine molecule with various protonated forms can act as a cation in energetic salts and provide abundant hydrogen bond donors and acceptors. Meanwhile, the plane of melamine can further Received: June 3, 2015 Accepted: December 7, 2015 Published: December 17, 2015 207

DOI: 10.1021/acs.jced.5b00458 J. Chem. Eng. Data 2016, 61, 207−212

Journal of Chemical & Engineering Data

Article

Scheme 1. Synthesis of 4,4′-Oxybis[3,3′-(1H-5-tetrazol)]furazan

Figure 1. (a) The asymmetric unit of compound 2. (b) The 2D net structure of compound 2. (c) The supramolecular structure of compound 2. (d) The π−π stacking interactions between tetrazole and tetrazole, furazan and furazan. (e) The π−π stacking interactions between tetrazole and tetrazole, furazan and furazan, and MA and furazan rings.

353 K. The resulting solution was filtered and kept at room temperature for crystallization. After 3 days, colorless block crystals of 2 were obtained in a yield of 76% (based on MA) and purity of 99.90% estimated by Fourier transformation nearinfrared spectroscopy. Anal. Calcd for C9H10N18O4 (434.35): C, 24.86; H, 2.30; N, 58.02. Found: C, 24.81; H, 2.23; N, 58.01. IR (KBr, cm−1): 3569 (w), 3416 (w), 3335 (w), 2858 (w), 2696 (m), 1613 (w), 1578 (m), 1496 (m), 1406 (s), 1226 (m), 1172 (s), 1082 (w), 1001 (m), 865 (m), 793 (m), 532 (s). 2.2. Rotating-Bomb Combustion Calorimetry. The constant-volume combustion energy was determined with a RBC-type II typed rotating-bomb calorimeter.25 The composition of the instrument and the specific experiment process were described in ref 25. The initial temperature of the combustion reaction was maintained at T = 298.1500 ± 0.0005 K, and the initial oxygen pressure was 2.5 MPa. In order to ensure better combustion, approximately 200 mg of the samples and 600 mg benzoic acid (SRM, 39i, NIST) were mixed and pressed to form a tablet. The energy equivalent of the calorimeter was calibrated following the procedure of Coops et al.26 Benzoic acid was used to be as the standard substance, which has an isothermal heat of combustion of −26434 ± 3 J·g−1 at 298.15 K. The energy equivalent of the calorimeter is 18533.01 ± 8.12 J·K−1, which was determined through six-times calibration experiment with an accuracy uncertainty of 4.38 × 10−4. The calibrated

stable compounds through π−π stacking interactions.24 Herein, the furazan derivative (1) and its energetic salt with melamine (MA), (MA+)·(HBTFOF¯)·H2O (2) were synthesized and characterized by IR spectroscopy, elemental analysis, mass spectrum, and single-crystal X-ray analysis. The stability of the compound 2 was characterized by TG, DSC, and DFT calculations. The standard molar enthalpy of formation of 2 was calculated from the determination of constant-volume combustion energy. Detonation performances (P, D) of 2 were calculated with the nitrogen equivalent equation. Sensitivity tests show that 2 is insensitive to external stimuli.

2. EXPERIMENTAL SECTION General caution: these compounds are energetic materials and tend to explode under certain conditions. Appropriate safety precautions (safety glasses, face shields, leather coat, and ear plugs) should be taken, especially when the compounds are prepared on a large scale. 2.1. Synthesis. 2.1.1. Synthesis of H2BTFOF (1). The compound 4,4′-oxybis[3,3′-(1H-5-tetrazol)]furazan (H2BTFOF) (1) was synthesized with 3-amino-4-cyanofurazan (CNAF) as the starting material, as shown in Scheme 1. The details of synthesis for H2BTFOF were provided in the Supporting Information. 2.1.2. Synthesis of (MA+)·(HBTFOF¯)·H2O (2). MA (63 mg, 0.5 mmol) was added to mixed solvent of water and ethanol (3:1, 20 mL) of H2BTFOF (145 mg, 0.5 mmol) with stirring at 208



Article

experimental results are listed in Supporting Information Table S1. The amount of nitric acid was determined by using Devarda’s alloy method,27 and correction was based on −59.7 kJ·mol−1 for the molar formation energy of the formed 0.1 mol·dm−3 of aqueous HNO3 on the basis of eq 1.The standard state correction (ΔU∑) was calculated by the procedures given by Hubbard et al.28 The correct value of the heat exchange was calculated according to eq 2.29 1 5 1 N2(g) + O2 (g) + H 2O(l) = HNO3(aq) 2 4 2 Δ(ΔT ) = nV0 +

Vn − V0 ⎛ T0 + Tn ⎜ + Tn̅ − T0̅ ⎜⎝ 2

(1)

n−1

⎞

i=1

⎠

∑ Ti − nT0̅ ⎟⎟

Figure 2. DSC and TG curve of compound 2.

(2)

where Δ(ΔT) denotes the correct value of the heat exchange, n is the number of readings for the main (or reaction) period, V0 and Vn are the rate of temperature change at the initial and final stages, respectively (V is positive when temperature decreased), T̅ 0 and T̅ n are the average temperatures of the calorimeter at the initial and final stages, respectively (average temperature for first and last reading), T0 is the last reading of the initial stage, Tn is the first reading of the final stage, Σi n−1 = 1 Ti the sum of all the readings, except for the last one of the main period, and (Vn − V0)/(T̅ 0 − T̅ n) is constant.

compound 2 involves two stages of weight loss. In the first stage, the weight loss of 4.28% in the range of (433 to 453) K corresponds to the loss of water molecules (calcd 4.14%). The second stage takes place in the temperature range of 501−773 K with the mass loss of 93.49%, which is in good agreement with the collapse of framework and decomposition of organic components. 3.3. Optimized Structure, Total Energy, and the Frontier Orbital Energy (hartree). The DFT-B3LYP/631+G(d) method was used to optimize the structure of the compound and compute its frequencies. Vibration analysis shows that the optimized structure is in accordance with the minimum points on the potential energy planes, which signifies no virtual frequencies, revealing that the obtained optimized structure is stable. Molecular total energy (Etotal), frontier orbital energy levels (EHOMO and ELUMO), and its gaps (ΔE) are −1634.882956, −0.25681, −0.06794, and 0.18887 hartree for 2. The large value of ΔE can be as an important parameter to express the stability of the energetic materials.30 The views of HOMO and LUMO are shown in Figure 3. For 2, the electron density of HOMO and LUMO are mainly focused on HBTFOF¯, and the electron density of HBTFOF¯ in HOMO is larger than that in LUMO, indicating HBTFOF¯ is activity of the component. 3.4. Nonisothermal Kinetics Analysis for the Dehydration Product of 2. In the present work, Kissinger’s method31 and Ozawa’s method32,33 are used to evaluate thermokinetics stability of the dehydrated product (MA+)· (HBTFOF¯). The apparent activation energy Ek and Eo, preexponential factor Ak and linear correlation coefficients Rk and Ro were achieved from original data, as shown in Table 1. 3.5. Oxygen-Bomb Calorimetry. A RBC-type II typed rotating-oxygen bomb calorimeter25 was used to measure the constant-volume energy of combustion of 2. On the basis of IR spectra, it is found that the IR spectra of the mixed sample and the pure sample are consistent except for a strong absorption peak 1683 cm−1 (CO) in the mixed sample. Obviously, there is no chemical reaction occurring between the benzoic acid and the compound 2 besides simple mixing. So the sample burnt in the calorimeter is chemically identical to the initial sample. The constant volume energy of combustion (ΔcU) of energetic compound 2 is listed in Table 2. On the basis of the formula ΔcHθm = ΔcU + ΔnRT, Δn = ng (products, g) − ng (reactants, g), (ng is the total molar amount of gases in the products or reactants, R = 8.314 J·mol−1·K−1, T = 298.15 K),

3. RESULTS AND DISCUSSION 3.1. X-ray Structure of (MA+)·(HBTFOF¯)·H2O (2). Single crystal X-ray diffraction analysis reveals there exists one MA+, one HBTFOF¯, and one water molecular in the asymmetric unit (Figure 1a). The proton transfer from the H2BTFOF to melamine is confirmed. The bond lengths O−N and N−N are on average 1.38 and 1.332 Å, respectively. The MA+ utilizes the amino group to form N−H···N hydrogen bonds [N16− H16B···N3 3.115(7), N16−H16B···N4 3.334(7), N15−H15··· N4 2.809(7), N18−H18B···N5 3.103(7), N17−H17A···N8 3.096(7) Å] with HBTFOF¯, resulting in the formation of hydrogen-bonded supramolecular chains, which are further extended into a two-dimensional (2D) sheet (Figure 1b) through three hydrogen bonds [N16−H16A···N6 3.069(7), N18−H18A···N11 3.536(7), N18−H18A···N10 3.069(7) Å] between each MA+ and HBTFOF¯ from neighboring chains. The water molecules of between layers and HBTFOF¯ form a strong hydrogen bond [O1W−H1B···O2 2.272(10) Å], which further can form the 3D supramolecular structure. Further analysis of the crystal packing suggests the existence of π−π stacking interactions between the double-layer arrays (Figure 1d,e) with the center-to-center distances of MA and furazan rings, tetrazole and tetrazole, and furazan and furazan, being 3.4632(8) to 3.5984(7) Å, respectively. 3.2. Thermal Decomposition. DSC and TG curves were used to show the thermal decomposition behaviors of 2. X-ray powder diffraction (XRPD) experiments have been performed to identify the phase purity of the compound 2. The experimental patterns and simulated ones have a good agreement, indicating the phase purity of the as-synthesized powder products (Supporting Information Figure S1). DSC and TG curves of compound 2 are depicted in Figure 2. As shown in DSC curve, there are one endothermic and one exothermic process for 2. The endothermic peak corresponds to the dehydration process. The exothermic peak reflects the main decomposition process. TG curve indicates that 209



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Figure 3. View of HOMO (left) and LUMO (right) for 2 by B3LYP/6-311+G(d).

± 6.30 kJ·mol−1. The standard molar enthalpy of formation of the combustion products CO2 (g), ΔfHθm (CO2, g) = −393.51 ± 0.13 kJ·mol−1, H2O (l), and Δf Hθm (H2O, l) = −285.83 ± 0.04 kJ·mol−1 were obtained from ref 34. 3.6. Heat of Detonation. According to the order of H2O, CO2, NH3, and C in forming detonation products,35 the detonation equation of 2 is given as eq 4

Table 1. Peak Temperatures of the Exothermic Processes at Different Heating Rates and the Thermokinetic Parametersa compound heating rate β (K·min−1) 2 5 8 10 Kissinger’s method Ek (kJ·mol−1) ln Ak (s−1) linear correlation coefficient (Rk) Ozawa-Doyle’s method Eo (kJ·mol−1) linear correlation coefficient (Ro)

2 peaks temperatures Tp (K) 537.35 544.95 548.35 550.35

C9H10N18O4 = 4H 2O +

297.10 26.49 0.9995

(4)

where density functional theory (DFT) was used to compute the energy of detonation (ΔEdet). ΔHdet is estimated by using a linear correlation equations (ΔHdet = 1.127 ΔEdet+ 0.046, r = 0.968).36,37 The calculated ΔEdet and ΔHdet are listed in Table 3. As shown in Table 3, the heat of detonation of 21.29 kJ·g−1 for compound 2 is far higher than those of TNT and RDX. 3.7. Detonation Velocity and Pressure. The detonation velocity (D) and pressure (P) of an explosive can be predicted with the nitrogen equivalent equation (NE equations).38 The detonation products and the corresponding nitrogen equivalent indices are listed in Table 4. NE equations are shown in eqs 5 to 7

291.12 0.9953

a Standard uncertainties u is u(Tp) = 0.01 K, and the combined expanded uncertainties Uc are Uc(Ek) = 0.01 kJ·mol−1, Uc(lnAk) = 0.01 s−1, Uc(Eo) = 0.01 kJ·mol−1. A is the pre-exponential factor; E is the apparent activation energy; Tp is the peak temperature; R is the gas constant, 8.314 J mol−1·K −1; β is the linear heating rate; and C is constant.

the standard molar enthalpy of combustion (ΔcHθm) can be derived as being −5489.29 ± 6.19 kJ·mol−1 for 2. The combustion reaction proceeds as eq 3

∑ N = 100 ∑

C9H10N18O4 (s) + 9.5O2 (g) = 9CO2 (g) + 5H 2O(l) + 9N2(g)

2 26 NH3 + 9C + N2 3 3

XiNi M

(5)

D = (690 + 1160ρ0 ) ∑ N

(3)

According to Hess’s law, the standard molar enthalpy of formation (ΔfHθm) of 2 at 298.15 K is calculated as being 518.55

(

P = 1.092 ρ0 ∑ N

2

)

(6)

− 0.574

(7)

Table 2. Constant-Volume Combustion Energy of the Compound 2 at T = 298.15 Ka no. 1 2 m1/g 0.20898 0.20102 m2/g 0.60125 0.60186 m/g 0.81023 0.80288 ΔTtest/K 1.0002 0.9969 ζ/K 0.0316 0.0296 ΔT/K 1.0318 1.0265 W/J·K−1 18533.01 ± 8.12 18533.01 ± 8.12 G/J·cm−1 0.9 0.9 b/cm 13 13 ΔU∑/J 53.01 49.82 ΔU(HNO3)/J 511.76 500.76 −ΔcU/J·g−1 12692.35 ± 31.46 12696.68 ± 32.48 −ΔcU = (x̅ ± Sx)̅ J·g−1= (12686.45 ± 14.25) J·g−1

3 0.20716 0.60117 0.80833 0.9991 0.0312 1.0303 18533.01 ± 8.12 0.9 12 52.34 510.49 12693.58 ± 31.68

4 0.20978 0.60120 0.81098 1.0004 0.0321 1.0325 18533.01 ± 8.12 0.9 14 53.89 515.73 12684.68 ± 31.37

5 0.20033 0.60149 0.80182 0.9963 0.0289 1.0252 18533.01 ± 8.12 0.9 14 49.02 496.87 12687.89 ± 32.55

6 0.20807 0.60169 0.80976 1.0006 0.0308 1.0314 18533.01 ± 8.12 0.9 13 51.89 517.62 12663.52 ± 31.58

a Standard uncertainties u are u(T) = 0.01 K, u(p) = 0.1 kPa, u(m) = 0.00001 g, u(ΔTtest) = 0.0001 K, u(ζ) = 0.0001 K, u(ΔT) = 0.0001 K, u(G) = 0.01 J·cm−1, u(b) = 1 cm, u(ΔU∑) = 0.01 J, u(ΔU(HNO3)) = 0.01 J, and relative standard uncertainties ur are ur(W) = 0.0004, ur(ΔcU) = 0.0011. m1 is the mass of compound 2; m2 is the mass of benzoic acid; m is the total of compound 2 and benzoic acid; ΔTtest is the measured temperature rise; ζ is the corrected temperature rise; ΔT is the total temperature rise; W is the energy equivalent of the calorimeter; G is the combustion enthalpy of Ni−Cr wire; b is the length of Ni−Cr wire; ΔU (HNO3) is the energy correction for the nitric acid formation; ΔUΣ is the standard state correction; ΔcU is the constant volume energy of combustion. Sx̅ = [Σni=1 σ2/n(n − 1)]1/2 in which n is the experimental number and σ is the uncertainty of measurement standard combustion enthalpy data.

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Table 3. Calculated Parameters Used in the Detonation Reaction compound 2

H2O

N2

C

NH3

ΔEdet

ΔEdet

ΔHdet

hartree

hartree

hartree

hartree

hatree

hartree

kJ·g−1

kJ·g−1

−1634.882956

−76.3776

−109.447

−37.738

−56.5045

3.5202

21.29

24.19

Table 4. Nitrogen Equivalents of Different Detonation Products detonation product nitrogen equivalent index

N2 1.00

H2O 0.54

CO2 1.35

in which ρ0 is the density of compound 2; ∑N is the nitrogen equivalent of the detonation products; Ni is the nitrogen equivalent index of certain detonation product; M is the the molecular mass; Xi is the mole number of certain detonation products produced by a mole explosives. According to eqs 4 to 7, in which M = 434.35 g·mol−1 and ρo = 1.6730g·cm−3, ∑N, D, and P of 2 can be obtained as follows

∑N =

100 × ⎡⎣4 × 0.54 +

2 3

× (− 0.0578) + 9 × 0.15 +

26 3

compound formula Mr (g·mol−1) IS (J)b FS (N)c N (%)d Ω (%)e Tdec (K)f ρo (g·cm−3)g ΔfHmθ (kJ·mol−1)h

× 1⎤⎦

434.35

D = (690 + 1160ρo ) ∑ N

2

2 C9H10N18O4 434.35 38 > 360 58.02 −69.99 501 1.6730 518.55 ± 6.30

TNT36,37 C7H5N3O6 227.13 15 353 18.50 −73.96 > 433 1.654 59.1

RDX36,37 C3H6N6O7 222.12 7.5 120 37.80 −21.60 483 1.800 70

Standard uncertainties u are u(T) = 0.01 K, u(p) = 0.1 kPa, u(Mr) = 0.01 g·mol−1, u(IS) = 0.1 J, u(FS) = 1 N, u(N) = 0.0001, u(Ω) = 0.0001, u(Tdec) = 0.1 K, and the combined expanded uncertainty Uc is Uc(ρo) = 0.0001 g·cm−3 (0.95 level of confidence) and relative standard uncertainty ur is ur(ΔfHmθ) = 0.012. bImpact sensitivity. c Friction sensitivity. dNitrogen content. eOxygen balance. fDecomposition temperature of the main framework. g Experimentally determined density at 298.15 K. hStandard enthalpy of formation determined experimentally at 298.15 K.

= 7234.90m·s−1

)

N−H −0.0578

a

= (690 + 1160 × 1.6730) × 2.7502

(

O2 0.50

Table 5. Physicochemical Properties of 2 and Classical Energetic Compounds at Temperature T = 298.15 K and Pressure p = 100 kPaa

= 2.7502

P = 1.092 ρ0 ∑ N

C 0.15

− 0.574

= 1.092 × (1.6730 × 2.7502)2 − 0.574 = 22.54Gpa

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3.8. Sensitivity Tests. The impact sensitivity value (h50) of the compound 2 is 194 cm which corresponds to the impact energies of 38 J. Under the same experimental condition, the impact sensitivity values of h50 for TNT is 77 cm (15.0 J).39 The friction sensitivity of compound 2 is not observed up to 36 kg, which is lower than that of RDX (12 kg).40 The physicochemical properties of compound 2 and classical energetic materials are listed in Table 5.

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.5b00458. Data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_ request/cif. Materials and instruments, the synthesis process of 4,4′oxybis[3,3′-(1H-5-tetrazol)]furazan (H2BTFOF), crystallographic data collection and refinement, the calibrated experimental results for the energy equivalent of the calorimeter using benzoic acid (Table S1), the crystal data and structure refinement details of 2 (Table S2), the selected bond lengths and bond angles of 2 (Table S3), the hydrogen-bonding lengths and angles for 2 (Table S4), temperature and sensitivity calibration of DSC using standard substance (Table S5), and PXRD curves of 2 (Figure S1). (PDF) CCDC number for 2, 1000210. (CIF)

4. CONCLUSION A new energetic compound, (MA+)·(HBTFOF¯)·H2O was prepared and characterized by IR spectrum, TG, DSC, and single-crystal X-ray diffraction. The constant-volume combustion energy of compound 2 was determined (−12686.45 ± 14.25) J·g−1 by a precision rotating-bomb combustion calorimeter at 298.15 K. The standard molar enthalpy of formation for compound 2 is calculated to be (518.55 ± 6.30) kJ·mol −1 . The dehydration product of 2 has a high decomposition temperature. For 2, the electron density of HOMO and LUMO are mainly focused on HBTFOF¯ and the electron density of HBTFOF¯ in HOMO is larger than that in LUMO, indicating HBTFOF¯ is activity of the component. The sensitivity measurements indicate that compound 2 is insensitive to external stimuli. The analysis results indicate compound 2 behaves as a potential HEDM with favorable safety.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Funding

We gratefully acknowledge financial support from the National Natural Science Foundation of China (Grant 21373162, 21473135, 21073142, and 21173168) and the Natural Science 211



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Foundation of Shanxi Province (Grant 11JS110, 2013JM2002, and SJ08B09). Notes

The authors declare no competing financial interest.

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