Energetic materials comprising perovskite compound ABX.SUB.3
10913693 ยท 2021-02-09
Assignee
Inventors
Cpc classification
C06B29/00
CHEMISTRY; METALLURGY
C06B31/00
CHEMISTRY; METALLURGY
International classification
C07D241/04
CHEMISTRY; METALLURGY
C06B29/00
CHEMISTRY; METALLURGY
C06B31/00
CHEMISTRY; METALLURGY
C06B43/00
CHEMISTRY; METALLURGY
Abstract
The present application belongs to the field of energetic compounds, and particularly relates to the use of a perovskite-type compound ABX.sub.3 as an energetic material. As a finding of the present application, the structural characteristics of the perovskite type enables the type of compound to be highly stable, thus overcoming the unsafety of an explosive having poor stability in the prior art. Meanwhile, the structural characteristics of the compound, such as rich energetic ligands, as well as the alternately arranged oxidizing energetic anions and reducing organic cations in the space, endow the compound with excellent performance on instantaneously releasing energy at detonation. The resulting three-dimensional structure allows the compound to not only have an energetic material effect but also overcome shortcomings of some existing energetic materials.
Claims
1. An energetic material comprising a perovskite type compound of formula: ABX.sub.3, wherein, A is: ##STR00003## B is Na.sup.+, K.sup.+, Rb.sup.+ or NH.sub.4.sup.+; and X is ClO.sub.4.sup. or NO.sub.3.sup..
2. The energetic material of claim 1, wherein: (1) A is: ##STR00004## B is Na.sup.+ or Rb.sup.+; and X is ClO.sub.4.sup.; or (2) A is: ##STR00005## B is K.sup.+ or NH.sub.4.sup.+; and X is NO.sub.3.sup.; or (3) A is: ##STR00006## and B is Na.sup.+.
3. The energetic material of claim 1, wherein A is: ##STR00007##
4. The energetic material of claim 1, wherein B is K.sup.+ or NH.sub.4.sup.+.
5. The energetic material of claim 1, wherein X is ClO.sub.4.sup..
6. The energetic material of claim 1, wherein: A is ##STR00008## B is Na.sup.+; and X is ClO.sub.4.sup..
7. The energetic material of claim 1, wherein: A is ##STR00009## B is K.sup.+; and X is ClO.sub.4.sup..
8. The energetic material of claim 1, wherein: A is ##STR00010## B is Rb.sup.+; and X is ClO.sub.4.sup..
9. The energetic material of claim 1, wherein: A is ##STR00011## B is NH.sub.4.sup.+; and X is ClO.sub.4.sup..
10. The energetic material of claim 1, wherein: A is ##STR00012## B is K.sup.+; and X is NO.sub.3.sup..
11. The energetic material of claim 1, wherein: A is ##STR00013## B is NH.sub.4.sup.+; and X is NO.sub.3.sup..
12. The energetic material of claim 1, wherein: A is ##STR00014## B is K.sup.+; and X is ClO.sub.4.sup..
13. The energetic material of claim 1, wherein: A is ##STR00015## B is NH.sub.4.sup.+; and X is ClO.sub.4.sup..
14. The energetic material of claim 1, wherein: A is ##STR00016## B is K.sup.+; and X is ClO.sub.4.sup..
15. The energetic material of claim 4, wherein: A is ##STR00017## B is NH.sub.4.sup.+; and X is ClO.sub.4.sup..
16. The energetic material of claim 1, wherein: A is ##STR00018## B is Na.sup.+; and X is ClO.sub.4.sup..
17. The energetic material of claim 1, wherein: A is ##STR00019## B is K.sup.+; and X is ClO.sub.4.sup..
18. The energetic material of claim 1, wherein: A is ##STR00020## B is NH.sub.4.sup.+; and X is ClO.sub.4.sup..
19. An explosive comprising the energetic material of claim 1.
20. A propellant comprising the energetic material of claim 1.
21. A rocket fuel comprising the energetic material of claim 1.
22. A safety air bag gas generant comprising the energetic material of claim 1.
23. A process for preparing an energetic material comprising a perovskite type compound of formula: ABX.sub.3, wherein, A is: ##STR00021## B is Na.sup.+, K.sup.+, Rb.sup.+ or NH.sub.4.sup.+; and X is ClO.sub.4.sup. or NO.sub.3.sup.; comprising the following steps: (i) adding a perchloric acid solution to a solution of 1,4-diazabicyclo[2.2.2]octane to form a mixture; and (ii) adding a sodium perchlorate solution to the mixture of step (i); or (iii) adding a perchloric acid solution to a solution of 1,4-diazabicyclo[2.2.2]octane to form a mixture; and (iv) adding a potassium perchlorate solution to the mixture of step (iii); or (v) adding a perchloric acid solution to a solution of 1,4-diazabicyclo[2.2.2]octane to form a mixture; and (vi) adding a rubidium perchlorate solution to the mixture of step (v); or (vii) adding a perchloric acid solution to a solution of 1,4-diazabicyclo[2.2.2]octane to form a mixture; and (viii) adding a ammonium perchlorate solution to the mixture of step (vii); or (ix) adding a perchloric acid solution to a solution of 1,4-diazabicyclo[2.2.2]octane 1,4-dioxide to form a mixture; and (x) adding a potassium perchlorate solution to the mixture of step (ix); or (xi) adding a perchloric acid solution to a solution of 1,4-diazabicyclo[2.2.2]octane 1-oxide to form a mixture; and (xii) adding a potassium perchlorate solution to the mixture of step (xi); or (xiii) adding ammonia to a perchloric acid solution to form a mixture; and (xiv) adding a solution of 1,4-diazabicyclo[2.2.2]octane 1,4-dioxide to the mixture of step (xiii); or (xv) adding a perchloric acid solution to a solution of piperazine to form a mixture; and (xvi) adding a sodium perchlorate solution to the mixture of step (xv); or (xvii) adding ammonia to a perchloric acid solution to form a mixture; and (xviii) adding a solution of piperazine to the mixture of step (xvii); or (xix) adding a nitric acid solution to a solution of 1,4-diazabicyclo[2.2.2]octane to form a mixture; and (xx) adding a potassium nitrate solution to the mixture of step (xix); or (xxi) adding ammonia to a nitric acid solution to form a mixture; and (xxii) adding a solution of 1,4-diazabicyclo[2.2.2]octane to the mixture of step (xxi).
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE INVENTION
(26) The inventor designs a series of perovskite type compounds having energetic groups, and makes relevant experiments and researches on the prospect of these compounds serving as novel high-performance explosives in the energetic field. In the present application, such perovskite type energetic compounds (ABX.sub.3, corresponding to an abbreviation DAP in the following embodiments and endowed with respective numbers) having the energetic ligands are provided. Experiments and calculations indicate that their energy densities and explosive performance may be comparable with those of high-performance active-duty military explosives RDX and HMX. Furthermore, the compounds have excellent safety performance, with non-volatile and non-hygroscopic characteristics, and are prepared from cheap and readily-available raw materials through a simple synthesis process. These compounds are novel energetic compounds having practical values in the energetic fields.
(27) The ABX.sub.3 may be synthesized by a synthesis method of the present application. A synthesis method (Z. M. Jin, Y. J. Pan, X. F. Li, M. L. Hu, L. Shen, Journal of Molecular Structure, 2003, 660, 67) of a perovskite type compound (C.sub.6H.sub.14N.sub.2)[K(ClO.sub.4).sub.3], which is disclosed by Z. M. Jin et al, may be also employed for reference.
(28) X in ABX.sub.3 is at least one anionic energetic ligand. The energetic ligand is an explosive ligand. Common explosive ligands include, but not limited to, ClO.sub.3.sup., ClO.sub.4.sup., IO.sub.4.sup., NO.sub.3.sup., ONC.sup., an azo ligand, an azides ion, nitryl and the like.
(29) In ABX.sub.3, for example, X may include one or more ions. For example, 2, 3, 4, 5, 6, 7, 8, 9, 10 . . . types of X ions may exist at the same time. The same is true for A and B. When perovskite includes more than one type of A cations, different A cations may be distributed at A sites in an ordered or disordered manner. When the perovskite includes more than one type of B cation, different B cations may be distributed at B sites in an ordered or disordered manner. When the perovskite includes more than one type of X anion, different X anions may be distributed at X sites in an ordered or disordered manner.
(30) Based on this nature, the above-mentioned X is at least one . . . ligand/ion, A is at least one . . . ligand/ion, B is at least one . . . ligand/ion, X is selected from . . . , A is selected from . . . , B is selected from . . . , etc. should be understood for example that for X, an ABX.sub.3 three-dimensional framework includes many X sites, each of which consists of one type of ions. In the three-dimensional framework, the multiple X sites may consist of the same type of ions, and also may consist of different types of ions. When the X sites consist of different ions, at least some sites (or most sites) are . . . ligands/ions. At this moment, such a situation that a few of sites in the whole ABX.sub.3 three-dimensional framework are not the . . . ligands/ions or some other foreign ions is not excluded as long as the number of these sites may not affect the overall performance to a large extent. The few of sites may, for example, have the mole number less than 50 percent, for example, not more than 40 percent, 30 percent, 25 percent, 20 percent, 15 percent, 10 percent, 9 percent, 8 percent, 7 percent, 6 percent, 5 percent, 4 percent, 3 percent, 2 percent or 1 percent. For A and B, it is the same.
(31) The present application performs various identification and characterization methods including powder X-ray diffraction identification, single-crystal structure characterization test, infrared spectral characterization, thermal stability characterization, differential scanning calorimetry (DSC), sensitivity characterization, and detonation heat/detonation pressure/detonation velocity calculation. There into, powder X-ray diffraction data under a room temperature condition are collected on a Bruker D8 Advance diffractometer by adopting a Cu-K ray. A scanning mode is as follows: : 2 linkage, stepping scanning, a 2 step length being 0.02. Single crystal X-ray diffraction data are collected on an Oxford Gemini S Ultra CCD diffractometer through a graphite monochromator in a co scanning manner by using a Mo-K X-ray. An SADABS program is adopted for absorption correction. A direct method is used for analysis, and then all non-hydrogen coordinates are calculated by using a differential Fourier function method and a least square method, and finally the structure is refined by using a full-matrix least-square technique. Organic hydrogen atoms are generated geometrically. The calculation work is completed on a PC by using Olex.sup.2 and SHELX program packages. Infrared spectral data are acquired on an IR Tensor 27 instrument. A dried sample and KBr are pressed into a transparent thin-sheet test sample. Thermogravimetric analysis is collected on a TA Q50 instrument in a nitrogen atmosphere at a scanning speed of 5 C./min. A DSC curve is collected on a TA DSC Q2000 instrument in the nitrogen atmosphere at the scanning speed of 5 C./min.
(32) The sensitivity characterization is to test impact, friction and thermal sensitivities according to the National Military Standards GJB772A-97 of the People's Republic of China. The impact sensitivity is tested by a 601.1 explosive probability method. The friction sensitivity is tested by a 602.1 explosive probability method. The thermal sensitivity is tested by a 606.1-burst point 5 s delay method. The electrostatic sensitivity is tested by the third section of the industrial initiating explosive material test method WJ/T 9038.3-2004: electrostatic-spark sensitivity test.
(33) At a room temperature, characteristic peaks of a perchlorate radical ligand in an infrared absorption spectrum are ranged from 1070 to 1100 cm.sup.1 (corresponding to asymmetric stretching vibration) and 617 to 637 cm.sup.1 (corresponding to asymmetric bending vibration). Characteristic peaks of a nitrate radical ligand in the infrared absorption spectrum are ranged from 1375 to 1390 cm.sup.1 (corresponding to asymmetric stretching vibration) and 845 to 860 cm.sup.1 (corresponding to asymmetric bending vibration).
(34) In one preferred embodiment, an adopted compound serving as an energetic material is (C.sub.6H.sub.14N.sub.2)[Na(ClO.sub.4).sub.3] (which is recorded as DAP-1), and is crystallized in the cubic space group Pa-3 at 223 K, with a cell length of 14.1537(1). An 26 angle locating the characteristic peaks of a powder X-ray diffraction pattern (Cu-K X-ray) of the compound at the room temperature is about: 12.30.5, 21.50.5, 24.90.5, 27.90.5, 35.60.5 and 37.20.5. A thermal stability analysis result shows that an explosion temperature of the compound may be up to 360 C. A differential scanning calorimetry result shows that heat released at 360 C. is 4398 J/g. A safety characterization result shows that DAP-1 is insensitive in impact sensitivity, friction sensitivity and electrostatic-spark sensitivity tests under the National Military Standards. Under the standard of Federal Institute for Material Research and Testing (BAM), the impact sensitivity of DAP-1 is about 17 J, and the friction sensitivity is about 36 N. The burst point of DAP-1 is 340 C. (5 s delay method). Detonation heat, detonation velocity and detonation pressure values obtained according to a Density Functional Theory (DFT) are respectively 1.53 kcal/g, 8.85 km/s and 37.31 GPa.
(35) In another preferred embodiment, an adopted compound serving as the energetic material is (C.sub.6H.sub.14N.sub.2)[K(ClO.sub.4).sub.3] (which is recorded as DAP-2), and is crystallized in the cubic space group Pa-3 at 223 K, with a cell length of 14.2910(1). An 2 angle locating the characteristic peaks of a powder X-ray diffraction pattern (Cu-K X-ray) of the compound at the room temperature is about: 12.150.5, 21.270.5, 24.630.5, 27.640.5, 35.200.5 and 36.890.5. A thermal stability analysis result shows that the explosion temperature of the compound may be 362 C. A differential scanning calorimetry result shows that heat released at 377 C. is 4076 J/g. A safety characterization result shows that under the standard of Federal Institute for Material Research and Testing (BAM), the impact sensitivity of DAP-2 is about 16 J, and the friction sensitivity is about 42 N. Detonation heat, detonation velocity and detonation pressure values obtained theoretically by the DFT are respectively 1.46 kcal/g, 8.64 km/s and 35.73 GPa.
(36) In another preferred embodiment, an adopted compound serving as the energetic material is (C.sub.6H.sub.14N.sub.2)[Rb(ClO.sub.4).sub.3] (which is recorded as DAP-3), and is crystallized in the cubic space group Pa-3 at 223 K, with a cell length of 14.453(2). An 2 angle locating the characteristic peaks of a powder X-ray diffraction pattern (Cu-K X-ray) of the compound at the room temperature is about: 12.00.5, 21.00.5, 24.30.5, 27.30.5, 34.70.5 and 36.40.5. A thermal stability analysis result shows that the explosion temperature of the compound may be up to 343 C. A differential scanning calorimetry result shows that heat released at 369 C. is 3797 J/g. A safety characterization result shows that under the standard of the Federal Institute for Material Research and Testing (BAM), the impact sensitivity of DAP-3 is about 22 J, and the friction sensitivity is about 28 N. Detonation heat, detonation velocity and detonation pressure values obtained theoretically by the DFT are respectively 1.33 kcal/g, 8.43 km/s and 35.14 GPa.
(37) In another preferred embodiment, an adopted compound serving as the energetic material is (C.sub.6H.sub.14N.sub.2)[NH.sub.4(ClO.sub.4).sub.3] (which is recorded as DAP-4), and is crystallized in the cubic space group Pa-3 at 223 K, with a cell length of 14.4264(1). An 2 angle locating the characteristic peaks of a powder X-ray diffraction pattern (Cu-K X-ray) diffraction of the compound at the room temperature is about: 12.00.5, 21.00.5, 24.40.5, 27.30.5, 34.80.5 and 36.50.5. A thermal stability analysis result shows that the explosion temperature of the compound may be up to 370 C. A differential scanning calorimetry result shows that heat released at 364 C. is 5177 J/g. A safety characterization result shows that under the standard of Federal Institute for Material Research and Testing (BAM), the impact sensitivity of DAP-4 is about 23 J, and the friction sensitivity is about 36 N.
(38) In another preferred embodiment, an adopted compound serving as the energetic material is (C.sub.6H.sub.14N.sub.2O.sub.2)[K(ClO.sub.4).sub.3] (which is recorded as DAP-O22), and is crystallized in the cubic space group Fm-3c at 298 K, with a cell length of 14.745(3). An 2 angle locating the characteristic peaks of a powder X-ray diffraction pattern (Cu-K X-ray) of the compound at the room temperature is about: 11.90.5, 20.80.5, 24.10.5, 27.00.5, 34.40.5 and 36.10.5. A thermal stability analysis result shows that a detonation temperature of the compound may be 354 C. A differential scanning calorimetry result shows that heat released at 358 C. is 5424 J/g. A safety characterization result shows that under the standard of the Federal Institute for Material Research and Testing (BAM), the impact sensitivity of DAP-O22 is about 11 J, and the friction sensitivity is about 14 N.
(39) In another preferred embodiment, an adopted compound serving as the energetic material is (C.sub.6H.sub.14N.sub.2O)[K(ClO.sub.4).sub.3] (which is recorded as DAP-O12). An 2 angle locating the characteristic peaks of a powder X-ray diffraction pattern (Cu-K X-ray) of the compound at the room temperature is about: 12.10.5, 21.10.5, 24.40.5, 27.30.5, 34.80.5 and 36.50.5. In another preferred embodiment, an adopted compound serving as the energetic material is (C.sub.6H.sub.14N.sub.2O.sub.2)[NH.sub.4(ClO.sub.4).sub.3] (which is recorded as DAP-O24). An 2 angle locating the characteristic peaks of a powder X-ray diffraction pattern (Cu-K X-ray) of the compound at the room temperature is about: 11.90.5, 20.80.5, 24.00.5, 27.00.5, 34.40.5 and 36.00.5. A differential scanning calorimetry result shows that heat released at 357 C. is 4632 J/g. A safety characterization result shows that under the standard of the Federal Institute for Material Research and Testing (BAM), the impact sensitivity of DAP-O24 is about 4 J, and the friction sensitivity is about 32 N.
(40) In another preferred embodiment, an adopted compound serving as the energetic material is (C.sub.4H.sub.12N.sub.2)[Na(ClO.sub.4).sub.3] (which is recorded as PAP-1). An 2 angle locating the characteristic peaks of a powder X-ray diffraction pattern (Cu-K X-ray) of the compound at the room temperature is about: 12.60.5, 21.70.5, 22.40.5, 22.70.5, 25.40.5, 26.80.5, 27.20.5, 37.70.5 and 38.40.5. A differential scanning calorimetry result shows that heat released at 375 C. is 4685 J/g. In another preferred embodiment, an adopted compound serving as the energetic material is (C.sub.4H.sub.12N.sub.2)[NH.sub.4(ClO.sub.4).sub.3] (which is recorded as PAP-4). A differential scanning calorimetry result shows that heat released at 356 C. is 3780 J/g.
(41) In another preferred embodiment, an adopted compound serving as the energetic material is (C.sub.6H.sub.14N.sub.2)[K(NO.sub.3).sub.3] (which is recorded as DAN-2). An 26 angle locating the characteristic peaks of a powder X-ray diffraction pattern (Cu-K X-ray) of the compound at the room temperature is about: 12.60.5, 17.90.5, 22.00.5, 25.50.5, 28.60.5, 31.30.5, 36.40.5, 38.70.5, 40.90.5 and 43.00.5. A differential scanning calorimetry result shows that heat released at 177 C. is 1222 J/g. A safety characterization result shows that under the standard of the Federal Institute for Material Research and Testing (BAM), the impact sensitivity of DAN-2 is about 29 J, and the friction sensitivity is more than 360 N.
(42) In another preferred embodiment, an adopted compound serving as the energetic material is (C.sub.6H.sub.14N.sub.2)[NH.sub.4(N.sub.3).sub.3] (which is recorded as DAN-4). An 2 angle locating the characteristic peaks of a powder X-ray diffraction pattern (Cu-K X-ray) of the compound at the room temperature is about: 10.30.5, 17.70.5, 20.40.5, 23.90.5, 24.80.5, 27.00.5, 29.70.5, 30.50.5, 32.20.5 and 37.00.5. A differential scanning calorimetry result shows that heat released at 170 C. is 1098 J/g.
Embodiment 1
(43) Synthesis and Test of (C.sub.6H.sub.14N.sub.2)[Na(ClO.sub.4).sub.3]
(44) Synthesis Method:
(45) 1) adding 112.88 g of 1,4-diazabicyclo[2.2.2]octane into 100 mL of water, then adding 360.00 g of a perchloric acid solution at a mass fraction of 70 to 72 percent, and stirring the mixture at a normal temperature for 5 minutes;
(46) 2) adding 140.52 g of monohydrate sodium perchlorate into 50 mL of water, and then stirring at the normal temperature to dissolve the monohydrate sodium perchlorate;
(47) 3) mixing the solutions obtained in steps 1) and 2), stirring the mixture for 30 minutes, and then filtering the mixture, washing residues with ethanol for three times, and performing vacuum drying on the washed residues to obtain a white powdery solid which is identified as perovskite type compound (C.sub.6H.sub.14N.sub.2)[Na(ClO.sub.4).sub.3] (No. DAP-1) with a yield of about 80 percent.
A Powder X-Ray Diffraction Identification Diagram:
(48) The powder X-ray diffraction diagram at the room temperature is as shown in
(49) TABLE-US-00001 TABLE 1 Characteristic peak values of powder X-ray diffraction of DAP-1 2/ d/ 12.3 7.22 18.6 4.78 21.5 4.14 24.9 3.58 25.7 3.47 27.9 3.20 28.6 3.12 33.8 2.65 35.6 2.52 36.1 2.48 37.2 2.41 37.8 2.38
Single-Crystal Structure Characterization Test:
(50) Detailed crystal test data are as shown in Table 2. A schematic diagram of a three-dimensional crystal structure is shown in
(51) TABLE-US-00002 TABLE 2 Single-crystal X-ray crystallographic data for DAP-1 Complex DAP-1 Formula C.sub.6H.sub.14Cl.sub.3N.sub.2NaO.sub.12 Formula weight 435.53 Temperature (K) 223 (2) Crystal system Cubic Space group Pa-3 a/ 14.1537 (1) V/.sup.3 2835.37 (4) Z 8 D.sub.c/g cm.sup.3 2.041 reflections collected 15434 unique reflections 1291 R.sub.int 0.0253 R.sub.1 [I > 2(I)].sup.[a] 0.0259 wR.sub.2 [I > 2(I)].sup.[b] 0.0681 R.sub.1 (all data) 0.0304 wR.sub.2 (all data) 0.0714 GOF on F.sup.2 1.057 Completeness (data) 0.996 .sup.[a]R.sub.1 = ||F.sub.o| |F.sub.c||/|F.sub.o|, .sup.[b]wR.sub.2 = {w[(F.sub.o).sup.2 (F.sub.c).sup.2].sup.2/w[(F.sub.o).sup.2].sup.2}.sup.1/2
Infrared Spectral Characterization of DAP-1:
(52) An infrared spectrum of DAP-1 is as shown in
(53) Thermal Stability Characterization of DAP-1:
(54) A thermogravimetric curve of DAP-1 is as shown in
(55) Differential Scanning Calorimeter (DSC) of DAP-1:
(56) A DSC curve of DAP-1 is as shown in
(57) Impact, Friction, Thermal and Electrostatic Sensitivity Characterization of DAP-1:
(58) Impact, friction and thermal sensitivity are tested according to the GJB772A-97 standard. The impact sensitivity is tested by a 601.1 explosive probability method. During the test (a hammer weight is 10 kg, and a drop height is 500 mm), the explosive probability of TNT is 9/25, but the explosive probability of DAP-1 is 0 percent. The friction sensitivity is tested by a 602.1 explosive probability method. During the test (2.45 MPa, and a swing angle of 80 degrees), the explosive probability of PETN is 2/25, but the explosive probability of DAP-1 is 0 percent. A thermal sensitivity test method is a 606.1 burst point 5 s-delay method. It measures that DAP-1 dramatically explodes at 340 C., which indicates that the burst point of DAP-1 is 340 C. An electrostatic sensitivity test method is the third section of an industrial initiating explosive material test method WJ/T 9038.3-2004: electrostatic spark sensitivity test. A half trigger voltage V.sub.50 of 25 mg of the test sample is 4.77 kV (a standard deviation is 0.21 kV), and half trigger energy E.sub.50 is 0.53 J, namely the electrostatic spark sensitivity of DAP-1 is 21.2 J.
(59) According to a test method of Federal Institute for Material Research and Testing (BAM), the impact sensitivity of DAP-1 is about 17 J, and the friction sensitivity is about 36 N.
(60) Detonation Heat, Detonation Pressure and Detonation Velocity Values of the Energetic Compound DAP-1 are Obtained Theoretically by the DFT:
(61) A decomposition heat value (decomposition enthalpy value H.sub.det) of DAP-1 is about 1.53 kcal/g calculated on the basis of the DFT (J. Am. Chem. Soc. 2012, 134, 1422), which is higher than those of active-duty energetic materials IMX (1.26 kcal/g) and RDX (1.27 kcal/g). An energy density is 3.11 kcal/cm.sup.3 obtained by conversion of a crystal density at 223 K, which is also higher than those of the active-duty energetic materials HMX (2.38 kcal/cm.sup.3) and RDX (2.29 kcal/cm.sup.3). According to a Kamlet-Jacob formula, DAP-1 has the detonation velocity of about 8.85 km/s and the detonation pressure of about 37.31 GPa, which are comparable to corresponding values of the active-duty energetic materials (HMX: the detonation velocity of 9.10 km/s and the detonation pressure of 39.50 GPa; RDX: the detonation velocity of 8.80 km/s and the detonation pressure of 33.80 GPa).
(62) The Amount of Gas Produced by DAP-1 Per Mole Number
(63) For judgment on products obtained by complete explosion of the energetic material in an oxygen-free environment, according to a document (J. Am. Chem. Soc. 2012, 134, 1422; J. Phys. Chem. A. 2014, 118, 4575; Chem. Eur. J. 2016, 22, 1141), final decomposition products include gaseous substances such as nitrogen, halogen hydride, water and carbon dioxide, and solid substances such as metal chlorides and elemental carbon (if oxygen atoms are not enough to completely convert all carbon atoms into the carbon dioxide). Therefore, 1 mole of DAP-1 may produce 12 moles of gas substances after complete explosion in the oxygen-free environment, with 3 moles of elemental carbon and 1 mole of solid sodium chloride remaining. Under a condition that an enough amount of oxidant (such as commonly used NH.sub.4ClO.sub.4) is mixed, DAP-1 per mole produces 1 mole of solid sodium chloride residues after complete explosion.
Embodiment 2
(64) Synthesis and Test of (C.sub.6H.sub.4N.sub.2)[K(ClO.sub.4).sub.3]
(65) Synthesis Method:
(66) 1) adding 2.24 g of 1,4-diazabicyclo[2.2.2]octane into 100 mL of water, then adding 5.74 g of a perchloric acid solution at a mass fraction of 70 to 72 percent, and stirring the mixture at a normal temperature for 5 minutes;
(67) 2) adding 2.77 of potassium perchlorate into 100 mL of water, and then heating and stirring the mixture to dissolve the potassium perchlorate.
(68) 3) mixing the solutions obtained in steps 1) and 2), stirring the mixture for 30 minutes, filtering the mixture, washing residues with ethanol for three times, and performing vacuum drying on washed residues to obtain a white powdery solid that is identified as perovskite type compound (C.sub.6H.sub.14N.sub.2)[K(ClO.sub.4).sub.3] (No. DAP-2) with the yield of about 90 percent.
A Powder X-Ray Diffraction Identification Diagram:
(69) The powder X-ray diffraction diagram at the room temperature is as shown in
(70) TABLE-US-00003 TABLE 3 Characteristic peak values of Powder X-ray diffraction of DAP-2 2/ d/ 11.9 7.43 12.2 7.28 17.3 5.12 21.3 4.17 23.8 3.73 24.63 3.61 27.6 3.23 35.2 2.55 36.9 2.43 37.4 2.40
Single-Crystal Structure Characterization Test:
(71) Detailed crystal test data are as shown in Table 4.
(72) TABLE-US-00004 TABLE 4 Single-crystal X-ray crystallographic data for DAP-2 Complex DAP-2 Formula C.sub.6H.sub.14Cl.sub.3N.sub.2KO.sub.12 Formula weight 451.64 Temperature (K) 223 (2) Crystal system Cubic Space group Pa-3 a/ 14.2910 (1) V/.sup.3 2918.69 (4) Z 8 D.sub.c/g cm.sup.3 2.056 reflections collected 5749 unique reflections 1254 R.sub.int 0.0348 R.sub.1 [I > 2(I)].sup.[a] 0.0285 wR.sub.2 [I > 2(I)].sup.[b] 0.0691 R.sub.1 (all data) 0.0394 wR.sub.2 (all data) 0.0761 GOF on F.sup.2 1.100 Completeness (data) 0.999 .sup.[a]R.sub.1 = F.sub.o| |F.sub.c/|F.sub.o|, .sup.[b]wR.sub.2 = {w[(F.sub.o).sup.2 (F.sub.c).sup.2].sup.2/w[(F.sub.o).sup.2].sup.2}.sup.1/2
Thermal Stability Characterization of DAP-2:
(73) A thermogravimetric curve of DAP-2 is as shown in
(74) Differential Scanning Calorimeter (DSC) of DAP-2:
(75) A DSC curve of DAP-2 is as shown in
(76) Impact and Friction Sensitivity Characterization of DAP-2:
(77) According to a test method of a Federal Institute for Material Research and Testing (BAM), the impact sensitivity of DAP-2 is about 16 J, and the friction sensitivity is about 42 N.
(78) Detonation Heat, Detonation Pressure and Detonation Velocity Values of the Energetic Compound DAP-2 Obtained Theoretically by the DFT:
(79) A decomposition heat value (decomposition enthalpy value H.sub.det) of DAP-2 is about 1.46 kcal/g calculated on the basis of the DFT (J. Am. Chem. Soc. 2012, 134, 1422), which is higher than those of active-duty energetic materials HMX (1.26 kcal/g) and RDX (1.27 kcal/g). An energy density is 3.01 kcal/cm.sup.3 obtained by conversion of a crystal density at 223 K, which is also higher than those of the active-duty energetic materials HMX (2.38 kcal/cm.sup.3) and RDX (2.29 kcal/cm.sup.3). According to a Kamlet-Jacob formula, DAP-2 has the detonation velocity of about 8.64 km/s and the detonation pressure of about 35.73 GPa.
(80) The Amount of Gas Produced by DAP-2 Per Mole Number
(81) For judgment on products obtained by complete explosion of the energetic material in an oxygen-free environment, according to a document (J. Am. Chem. Soc. 2012, 134, 1422; J. Phys. Chem. A. 2014, 118, 4575; Chem. Eur. J. 2016, 22, 1141), final decomposition products include gaseous substances such as nitrogen, halogen hydride, water and carbon dioxide, and solid substances such as metal chlorides and elemental carbon (if oxygen atoms are not enough to completely convert all carbon atoms into the carbon dioxide). Therefore, 1 mole of DAP-2 may produce 12 moles of gas substances after complete explosion in the oxygen-free environment, with 3 moles of elemental carbon and 1 mole of solid potassium chloride remaining. Under a condition that an enough amount of oxidant (such as commonly used NH.sub.4ClO.sub.4) is mixed, DAP-2 per mole produces 1 mole of solid potassium chloride residues after complete explosion.
Embodiment 3
(82) Synthesis and Test of (C.sub.6H.sub.14N.sub.2)[Rb(CO.sub.4).sub.3]
(83) Synthesis Method:
(84) 1) adding 2.24 g of 1,4-diazabicyclo[2.2.2]octane into 100 mL of water, then adding 5.74 g of a perchloric acid solution at a mass fraction of 70 to 72 percent, and stirring the mixture at a normal temperature for 5 minutes;
(85) 2) adding 3.70 of rubidium perchlorate into 100 mL of water, and then heating and stirring the mixture to dissolve the rubidium perchlorate;
(86) 3) mixing the solutions obtained in steps 1) and 2), stirring the mixture for 30 minutes, filtering the mixture, washing residues with ethanol for three times, and performing vacuum drying on the washed residues to obtain a white powdery solid that is identified as perovskite type compound (C.sub.6H.sub.14N.sub.2)[Rb(ClO.sub.4).sub.3] (No. DAP-3) with the yield of about 85 percent.
A Powder X-Ray Diffraction Identification Diagram:
(87) The powder X-ray diffraction diagram at the room temperature is as shown in
(88) TABLE-US-00005 TABLE 5 Characteristic peak values of powder X-ray diffraction of DAP-3 2/ d/ 12.0 7.36 17.1 5.19 21.0 4.23 23.6 3.77 24.3 3.66 27.3 3.27 27.0 2.98 34.7 2.58 36.4 2.47 36.9 2.43 39.0 2.31
Single-Crystal Structure Characterization Test:
(89) Detailed crystal test data are as shown in Table 6.
(90) TABLE-US-00006 TABLE 6 Single-crystal X-ray crystallographic data for DAP-3 Complex DAP-3 Formula C.sub.6H.sub.14Cl.sub.3N.sub.2RbO.sub.12 Formula weight 498.01 Temperature (K) 223 (2) Crystal system Cubic Space group Pa-3 a/ 14.453 (2) V/.sup.3 3018.9 (7) Z 8 D.sub.c/Ig cm.sup.3 2.191 reflections collected 14540 unique reflections 978 R.sub.int 0.0463 R.sub.1 [I > 2(I)].sup.[a] 0.0254 wR.sub.2 [I > 2(I)].sup.[b] 0.0669 R.sub.1 (all data) 0.0262 wR.sub.2 (all data) 0.0676 GOF on F.sup.2 1.078 Completeness (data) 0.996 .sup.[a]R.sub.1 = F.sub.o| |F.sub.c/|F.sub.o|, .sup.[b]wR.sub.2 = {w[(F.sub.o).sup.2 (F.sub.c).sup.2].sup.2/w[(F.sub.o).sup.2].sup.2}.sup.1/2
Thermal Stability Characterization of DAP-3:
(91) A thermogravimetric curve of DAP-3 is as shown in
(92) Differential Scanning Calorimeter (DSC) of DAP-3:
(93) A DSC curve of DAP-3 is as shown in
(94) Impact and Friction Sensitivity Characterization of DAP-3:
(95) According to a test method of a Federal Institute for Material Research and Testing (BAM), the impact sensitivity of DAP-3 is about 22 J, and the friction sensitivity is about 28 N.
(96) Detonation Heat, Detonation Pressure and Detonation Velocity Values of the Energetic Compound DAP-3 Obtained Theoretically by the DFT:
(97) A decomposition heat value (decomposition enthalpy value H.sub.det) of DAP-3 is about 1.33 kcal/g calculated on the basis of the DFT (J. Am. Chem. Soc. 2012, 134, 1422), which is higher than those of active-duty energetic materials HMX (1.26 kcal/g) and RDX (1.27 kcal/g). An energy density is 2.92 kcal/cm.sup.3 obtained by conversion of a crystal density at 223 K, which is also higher than those of the active-duty energetic materials HMX (2.38 kcal/cm.sup.3) and RDX (2.29 kcal/cm.sup.3). According to a Kamlet-Jacob formula, DAP-3 has the detonation velocity of about 8.43 km/s and the detonation pressure of about 35.14 GPa.
(98) The Amount of Gas Produced by DAP-3 Per Mole Number
(99) For judgment on products obtained by complete explosion of the energetic material in an oxygen-free environment, according to a document (J. Am. Chem. Soc. 2012, 134, 1422; J. Phys. Chem. A. 2014, 118, 4575; Chem. Eur. J. 2016, 22, 1141), final decomposition products include gaseous substances such as nitrogen, halogen hydride, water and carbon dioxide, and solid substances such as metal chlorides and elemental carbon (if oxygen atoms are not enough to completely convert all carbon atoms into the carbon dioxide). Therefore, 1 mole of DAP-3 may produce 12 moles of gas substances after complete explosion in the oxygen-free environment, with 3 moles of elemental carbon and 1 mole of solid rubidium chloride remaining. Under a condition that an enough amount of oxidant (such as commonly used NH.sub.4ClO.sub.4) is mixed, DAP-3 per mole produces 1 mole of solid rubidium chloride residues after complete explosion.
Embodiment 4
(100) Synthesis and Test of (C.sub.6H.sub.14N.sub.2)[NH.sub.4(ClO.sub.4).sub.3]
(101) Synthesis Method:
(102) 1) adding 2.24 g of 1,4-diazabicyclo[2.2.2]octane into 5 mL of water, then adding 5.74 g of a perchloric acid solution at a mass fraction of 70 to 72 percent, and stirring the mixture at a normal temperature for 5 minutes;
(103) 2) adding 2.35 g of ammonium perchlorate into 10 mL of water, and then stirring the mixture at the normal temperature to dissolve the ammonium perchlorate;
(104) 3) mixing the solutions obtained in steps 1) and 2), stirring the mixture for 10 minutes, filtering the mixture, washing residues with ethanol for three times, and performing vacuum drying on washed residues to obtain a white powdery solid that is identified as perovskite type compound (C.sub.6H.sub.4N.sub.2)[NH.sub.4(ClO.sub.4).sub.3] (No. DAP-4) with the yield of about 90 percent.
A Powder X-Ray Diffraction Identification Diagram:
(105) The powder X-ray diffraction diagram at the room temperature is as shown in
(106) TABLE-US-00007 TABLE 7 Characteristic peak values of powder X-ray diffraction of DAP-4 2/ d/ 12.0 7.35 21.0 4.22 22.0 4.05 23.5 3.78 23.7 3.75 24.4 3.65 27.3 3.26 34.8 2.58 36.5 2.46 37.0 2.43
Single-Crystal Structure Characterization Test:
(107) Detailed crystal test data are as shown in Table 8.
(108) TABLE-US-00008 TABLE 8 Crystal test data of DAP-4 Complex DAP-4 Formula C.sub.6H.sub.18Cl.sub.3N.sub.3O.sub.12 Formula weight 430.56 Temperature (K) 223 (2) Crystal system Cubic Space group Pa-3 a/ 14.4264 (1) V/.sup.3 3002.44 (4) Z 8 D.sub.c/g cm.sup.3 1.887 reflections collected 13016 unique reflections 1609 R.sub.int 0.0353 R.sub.1 [I > 2(I)].sup.[a] 0.0323 wR.sub.2 [I > 2(I)].sup.[b] 0.1127 R.sub.1 (all data) 0.0378 wR.sub.2 (all data) 0.1167 GOF on F.sup.2 0.9792 Completeness (data) 1.000 .sup.[a]R.sub.1 = F.sub.o| |F.sub.c/|F.sub.o|, .sup.[b]wR.sub.2 = {w[(F.sub.o).sup.2 (F.sub.c).sup.2].sup.2/w[(F.sub.o).sup.2].sup.2}.sup.1/2
Thermal Stability Characterization of DAP-4:
(109) A thermogravimetric curve of DAP-4 is as shown in
(110) Differential Scanning Calorimeter (DSC) of DAP-4:
(111) A DSC curve of DAP-4 is as shown in
(112) Impact and Friction Sensitivity Characterization of DAP-4:
(113) According to a test method of a Federal Institute for Material Research and Testing (BAM), the impact sensitivity of DAP-4 is about 23 J, and the friction sensitivity is about 36 N.
(114) The Amount of Gas Produced by DAP-4 Per Mole Number
(115) For judgment on products obtained by complete explosion of the energetic material in an oxygen-free environment, according to a document (J. Am. Chem. Soc. 2012, 134, 1422; J. Phys. Chem. A. 2014, 118, 4575; Chem. Eur. J. 2016, 22, 1141), final decomposition products include gaseous substances such as nitrogen, halogen hydride, water and carbon dioxide, and solid substances such as elemental carbon (if oxygen atoms are not enough to completely convert all carbon atoms into the carbon dioxide). Therefore, 1 mole of DAP-4 may produce 14.25 moles of gas substances after complete explosion in the oxygen-free environment, with 3.75 moles of elemental carbon remaining. Under a condition that an enough amount of oxidant (such as commonly used NH.sub.4ClO.sub.4) is mixed, DAP-4 produces no solid residues after complete explosion.
Embodiment 5
(116) Synthesis and Test of (C.sub.6H.sub.14N.sub.2O.sub.2)[K(ClO.sub.4).sub.3]
(117) Synthesis Method:
(118) 1) putting 1.01 g of 1,4-diazabicyclo[2.2.2]octane into a flask, gradually adding 6.0 g of hydrogen peroxide at a mass fraction of 30 percent for full reaction, thus obtaining an aqueous solution of 1,4-diazabicyclo[2.2.2]octane 1,4-dioxide, then adding 2.64 g of a perchloric acid solution at a mass fraction of 70 to 72 percent, and stirring the mixture for 20 minutes;
2) adding 0.42 g of potassium perchlorate into 20 mL of water, then heating the mixture until it is boiling, and stirring the mixture to dissolve the potassium perchlorate;
3) mixing the solutions obtained in steps 1) and 2), stirring the mixture for 10 minutes, and standing the mixture to gradually produce crystals; filtering the crystals, and washing residues with ethanol for three times; and performing vacuum drying on washed residues to obtain a white powdery solid that is identified as perovskite type compound (C.sub.6H.sub.14N.sub.2O.sub.2)[K(ClO.sub.4).sub.3] (DAP-O22) at the yield of about 55 percent.
A Powder X-Ray Diffraction Identification Diagram:
(119) The powder X-ray diffraction diagram at the room temperature is as shown in
(120) TABLE-US-00009 TABLE 9 Characteristic peak values of powder X-ray diffraction of DAP-O22 2/ d/ 11.9 7.41 17.0 5.22 20.8 4.26 24.1 3.69 27.0 3.29 28.2 3.16 34.4 2.60 36.1 2.49 36.6 2.45 38.4 2.34
Single-Crystal Structure Characterization Test:
(121) Detailed crystal test data are as shown in Table 10.
(122) TABLE-US-00010 TABLE 10 Crystal test data of DAP-O22 Complex DAP-O22 Formula C.sub.6H.sub.14Cl.sub.3N.sub.2KO.sub.14 Formula weight 469.53 Temperature (K) 298 (2) Crystal system Cubic Space group Fm-3c a/ 14.745 (3) V/.sup.3 3205.78 Z 8 D.sub.c/g cm.sup.3 1.946 reflections collected 606 unique reflections 154 R.sub.int 0.0265 R.sub.1 [I > 2(I)].sup.[a] 0.0427 wF.sub.2 [I > 2(I)].sup.[b] 0.1022 R.sub.1 (all data) 0.0658 wF.sub.2 (all data) 0.1172 GOF on F.sup.2 1.066 Completeness (data) 0.911 .sup.[a]R.sub.1 = F.sub.o| |F.sub.c/|F.sub.o|, .sup.[b]wR.sub.2 = {w[(F.sub.o).sup.2 (F.sub.c).sup.2].sup.2/w[(F.sub.o).sup.2].sup.2}.sup.1/2
Thermal Stability Characterization of DAP-O22:
(123) A thermogravimetric curve of DAP-O22 is as shown in
(124) Differential Scanning Calorimeter (DSC) of DAP-O22:
(125) A DSC curve of DAP-O22 is as shown in
(126) Impact and Friction Sensitivity Characterization of DAP-O22:
(127) According to a test method of a Federal Institute for Material Research and Testing (BAM), the impact sensitivity of DAP-O22 is about 11 J, and the friction sensitivity is about 14 N.
(128) The Amount of Gas Produced by DAP-O22 Per Mole Number
(129) For judgment on products obtained by complete explosion of the energetic material in an oxygen-free environment, according to a document (J. Am. Chem. Soc. 2012, 134, 1422; J. Phys. Chem. A. 2014, 118, 4575; Chem. Eur. J. 2016, 22, 1141), final decomposition products include gaseous substances such as nitrogen, halogen hydride, water and carbon dioxide, and solid substances such as metal chlorides and elemental carbon (if oxygen atoms are not enough to completely convert all carbon atoms into the carbon dioxide). Therefore, 1 mole of DAP-O22 may produce 13 moles of gas substances after complete explosion in the oxygen-free environment, with 2 moles of elemental carbon and 1 mole of solid potassium chloride remaining. Under a condition that an enough amount of oxidant (such as commonly used NH.sub.4ClO.sub.4) is mixed, DAP-O22 per mole produces 1 mole of solid potassium chloride residues after complete explosion.
Embodiment 6
(130) Synthesis and Test of (C.sub.6H.sub.14N.sub.2O)[K(ClO.sub.4).sub.3]
(131) Synthesis Method:
(132) 1) putting 1.01 g of 1,4-diazabicyclo[2.2.2]octane into a flask for continuous ice bathing, gradually and slowly adding 2.0 g of hydrogen peroxide at a mass fraction of 30 percent, thus obtaining an aqueous solution of 1,4-diazabicyclo[2.2.2]octane 1-oxide, then adding 2.64 g of a perchloric acid solution at a mass fraction of 70 to 72 percent, and stirring the mixture for 20 minutes;
2) adding 0.42 g of potassium perchlorate into 20 mL of water, then heating the mixture until it is boiling, and stirring the mixture to dissolve the potassium perchlorate;
3) mixing the solutions obtained in steps 1) and 2), stirring the mixture for 10 minutes and standing the mixture to gradually produce crystals; filtering the crystals, and washing residues with ethanol for three times, and performing vacuum drying on the washed residues to obtain a white powdery solid that is identified as perovskite type compound (C.sub.6H.sub.14N.sub.2O)[K(ClO.sub.4).sub.3] (DAP-O12) with the yield of about 30 percent.
A Powder X-Ray Diffraction Identification Graph:
(133) The powder X-ray diffraction graph at the room temperature is as shown in
(134) TABLE-US-00011 TABLE 11 Characteristic peak values of powder X-ray diffraction of DAP-O12 2/ d/ 12.1 7.33 17.1 5.18 21.1 4.22 24.4 3.64 27.3 3.26 28.2 3.17 34.8 2.58 36.5 2.46 37.1 2.42 38.4 2.34 39.8 2.26
The Amount of Gas Produced by DAP-O12 Per Mole Number
(135) For judgment on products obtained by complete explosion of the energetic material in an oxygen-free environment, according to a document (J. Am. Chem. Soc. 2012, 134, 1422; J. Phys. Chem. A. 2014, 118, 4575; Chem. Eur. J. 2016, 22, 1141), final decomposition products include gaseous substances such as nitrogen, halogen hydride, water and carbon dioxide, and solid substances such as metal chlorides and elemental carbon (if oxygen atoms are not enough to completely convert all carbon atoms into the carbon dioxide). Therefore, 1 mole of DAP-O12 may produce 12.5 moles of gas substances after complete explosion in the oxygen-free environment, with 2.5 moles of elemental carbon and 1 mole of solid potassium chloride remaining. Under a condition that an enough amount of oxidant (such as commonly used NH.sub.4ClO.sub.4) is mixed, DAP-O12 per mole produces 1 mole of solid potassium chloride residues after complete explosion.
Embodiment 7
(136) Synthesis and Test of (C.sub.6H.sub.14N.sub.2O.sub.2)[NH.sub.4(ClO.sub.4).sub.3]
(137) Synthesis Method:
(138) 1) putting 0.34 g of 1,4-diazabicyclo[2.2.2]octane into a flask, gradually and slowly adding 0.69 g of hydrogen peroxide at a mass fraction of 30 percent at a normal temperature, thus obtaining an aqueous solution of 1,4-diazabicyclo[2.2.2]octane 1,4-dioxide, then adding 0.86 g of a perchloric acid solution at a mass fraction of 70 to 72 percent, and stirring the mixture for 20 minutes;
2) adding 0.41 g of potassium perchlorate into 20 mL of water, stirring the mixture to dissolve the potassium perchlorate;
3) mixing the solutions obtained in steps 1) and 2), stirring the mixture for 10 minutes, and standing the mixture to gradually produce crystals; filtering the crystals, and washing residues with ethanol for three times; and performing vacuum drying on the washed residues to obtain a white powdery solid that is identified as perovskite type compound (C.sub.6H.sub.14N.sub.2O.sub.2)[NH.sub.4(ClO.sub.4).sub.3] (DAP-O24) at the yield of about 30 percent.
A Powder X-Ray Diffraction Identification Diagram:
(139) The powder X-ray diffraction diagram at the room temperature is as shown in
(140) TABLE-US-00012 TABLE 12 Characteristic peak values of powder X-ray diffraction of DAP-O24 2/ d/ 11.9 7.46 20.8 4.27 23.4 3.80 24.0 3.70 27.0 3.30 29.6 3.02 34.4 2.61 36.0 2.49 36.5 2.46 38.4 2.34
Differential Scanning Calorimeter (DSC) of DAP-O24:
(141) A DSC curve of DAP-O24 is as shown in
(142) Impact and Friction Sensitivity Characterization of DAP-O24:
(143) According to a test method of a Federal Institute for Material Research and Testing (BAM), the impact sensitivity of DAP-O24 is about 4 J, and the friction sensitivity is about 32 N.
(144) The Amount of Gas Produced by DAP-O24 Per Mole Number
(145) For judgment on products obtained by complete explosion of the energetic material in an oxygen-free environment, according to a document (J. Am. Chem. Soc. 2012, 134, 1422; J. Phys. Chem. A. 2014, 118, 4575; Chem. Eur. J. 2016, 22, 1141), final decomposition products include gaseous substances such as nitrogen, halogen hydride, water and carbon dioxide, and solid substances such as elemental carbon (if oxygen atoms are not enough to completely convert all carbon atoms into the carbon dioxide). Therefore, 1 mole of DAP-O24 may produce 15.25 moles of gas substances after complete explosion in the oxygen-free environment, with 2.75 moles of elemental carbon remaining. Under a condition that an enough amount of oxidant (such as commonly used NH.sub.4ClO.sub.4) is mixed, DAP-O24 produces no solid residues after complete explosion.
Embodiment 8
(146) Synthesis and Test of (C.sub.4H.sub.12N.sub.2)[Na(ClO.sub.4).sub.3]
(147) Synthesis Method:
(148) 1) adding 0.87 g of piperazine into 6 mL of water, then adding 1.7 mL of a perchloric acid solution at a mass fraction of 70 to 72 percent, and stirring the mixture at a normal temperature for 5 minutes;
(149) 2) adding 1.24 g of sodium perchlorate into 7 mL of water, stirring the mixture at the normal temperature to dissolve the sodium perchlorate;
(150) 3) mixing the solutions obtained in steps 1) and 2); heating the mixture to concentrate it; stirring the concentrated mixture for 30 minutes; filtering the mixture, and washing residues with ethanol for three times; and performing vacuum drying on the residues to obtain a white powdery solid that is identified as perovskite type compound (C.sub.4H.sub.12N.sub.2)[Na(ClO.sub.4).sub.3] (No. PAP-1) with the yield of about 50 percent.
A Powder X-Ray Diffraction Identification Diagram:
(151) The powder X-ray diffraction diagram at the room temperature is as shown in
(152) TABLE-US-00013 TABLE 13 Characteristic peak values of powder X-ray diffraction of PAP-1 2/ d/ 12.6 7.01 21.7 4.09 22.4 3.96 22.7 3.92 24.0 3.70 25.4 3.51 26.8 3.32 27.2 3.27 37.7 2.38 38.4 2.34
Single-Crystal Structure Characterization Test:
(153) Detailed crystal test data are as shown in Table 14.
(154) TABLE-US-00014 TABLE 14 Crystal test data of PAP-1 Complex PAP-1 Formula C.sub.4H.sub.12Cl.sub.3N.sub.2NaO.sub.12 Formula weight 409.49 Temperature (K) 298 (2) Crystal system Monoclinic Space group P2.sub.1/c a/ 10.1689 (4) b/ 9.7312 (4) c/ 13.2985 (6) / 91.993 (4) V/.sup.3 1315.17 (9) Z 4 D.sub.c/g cm.sup.3 2.068 reflections collected 11329 unique reflections 2722 R.sub.int 0.1187 R.sub.1 [I > 2(I)].sup.[a] 0.0731 wR.sub.2 [I > 2(I)].sup.[b] 0.2007 R.sub.1 (all data) 0.0788 wR.sub.2 (all data) 0.2103 GOF on F.sup.2 1.0292 Completeness (data) 0.9742 .sup.[a]R.sub.1 = F.sub.o| |F.sub.c/|F.sub.o|, .sup.[b]wR.sub.2 = {w[(F.sub.o).sup.2 (F.sub.c).sup.2].sup.2/w[(F.sub.o).sup.2].sup.2}.sup.1/2
Thermal Stability Characterization of PAP-1:
(155) A thermogravimetric curve of PAP-1 is as shown in
(156) Differential Scanning Calorimeter (DSC) of PAP-1:
(157) A DSC curve of PAP-1 is as shown in
(158) The Amount of Gas Produced by PAP-1 Per Mole Number
(159) For judgment on products obtained by complete explosion of the energetic material in an oxygen-free environment, according to a document (J. Am. Chem. Soc. 2012, 134, 1422; J. Phys. Chem. A. 2014, 118, 4575; Chem. Eur. J. 2016, 22, 1141), final decomposition products include gaseous substances such as nitrogen, halogen hydride, water and carbon dioxide, and solid substances such as metal chlorides and elemental carbon (if oxygen atoms are not enough to completely convert all carbon atoms into the carbon dioxide). Therefore, 1 mole of PAP-1 may produce 11.5 moles of gas substances after complete explosion in the oxygen-free environment, with 0.5 moles of elemental carbon and 1 mole of solid sodium chloride remaining. Under a condition that an enough amount of oxidant (such as commonly used NH.sub.4ClO.sub.4) is mixed, PAP-1 per mole produces 1 mole of solid sodium chloride residues after complete explosion.
Embodiment 9
(160) Synthesis and Test of (C.sub.4H.sub.12N.sub.2)[NH.sub.4(ClO.sub.4).sub.3]
(161) Synthesis Method:
(162) 1) adding 0.8 mL of ammonia water into 0.9 mL of a perchloric acid solution at a mass fraction of 70 to 72 percent, stirring the mixture at a normal temperature for 5 minutes, and then adding 1.6 mL of the perchloric acid solution at the mass fraction of 70 to 72 percent;
2) adding a proper amount of water into 0.87 g of piperazine, and stirring at the normal temperature to dissolve the piperazine;
3) mixing the solutions obtained in steps 1) and 2); heating the mixture to concentrate it; and stirring the concentrated mixture for 30 minutes; filtering the mixture, and washing residues with ethanol for three times; and performing vacuum drying on the washed residues to obtain a white powdery solid that is identified as perovskite type compound (C.sub.4H.sub.12N.sub.2)[NH.sub.4(ClO.sub.4).sub.3] (No. PAP-4) with the yield of about 40 percent.
Differential Scanning Calorimeter (DSC) of PAP-4:
(163) A DSC curve of PAP-1 is as shown in
(164) The Amount of Gas Produced by PAP-4 Per Mole Number
(165) For judgment on products obtained by complete explosion of the energetic material in an oxygen-free environment, according to a document (J. Am. Chem. Soc. 2012, 134, 1422; J. Phys. Chem. A. 2014, 118, 4575; Chem. Eur. J. 2016, 22,1141), final decomposition products include gaseous substances such as nitrogen, halogen hydride, water and carbon dioxide, and solid substances such as metal chlorides and elemental carbon (if oxygen atoms are not enough to completely convert all carbon atoms into the carbon dioxide). Therefore, 1 mole of PAP-4 may produce 13.75 moles of gas substances after complete explosion in the oxygen-free environment, with 1.25 moles of elemental carbon remaining. Under a condition that an enough amount of oxidant (such as commonly used NH.sub.4ClO.sub.4) is mixed, PAP-4 per mole produces no solid residues after complete explosion.
Embodiment 10
(166) Synthesis and Test of (C.sub.6H.sub.14N.sub.2)[K(NO.sub.3).sub.3]
(167) Synthesis Method:
(168) 1) adding 1.12 g of 1,4-diazabicyclo[2.2.2]octane into a proper amount of water, then adding 1.4 mL of a nitric acid solution at a mass fraction of 65 percent, and stirring the mixture at a normal temperature for 5 minutes;
(169) 2) adding 1.01 g of potassium nitrate into a proper amount of water, and stirring the mixture at the normal temperature to dissolve the potassium nitrate;
(170) 3) mixing the solutions obtained in steps 1) and 2), stirring and filtering the mixture, washing residues with ethanol for three times, and performing vacuum drying on the washed residues to obtain a white powdery solid that is identified as perovskite type compound (C.sub.6H.sub.4N.sub.2)[K(NO.sub.3).sub.3](No. DAN-2) at the yield of about 50 percent.
A Powder X-Ray Diffraction Identification Diagram:
(171) The powder X-ray diffraction diagram at the room temperature is as shown in
(172) TABLE-US-00015 TABLE 15 Characteristic peak values of powder X-ray diffraction of DAN-2 2/ d/ 12.6 7.01 17.9 4.94 22.0 4.03 25.5 3.49 28.6 3.12 31.3 2.85 36.4 2.47 38.7 2.32 40.9 2.21 43.0 2.10
Single-Crystal Structure Characterization Test:
(173) Detailed crystal test data are as shown in Table 16.
(174) TABLE-US-00016 TABLE 16 Single-crystal X-ray crystallographic data for DAN-2 Complex DAN-2 Formula C.sub.6H.sub.14N.sub.5KO.sub.9 Formula weight 339.32 Temperature (K) 298 (2) Crystal system Cubic Space group Pm-3m a/ 6.9512 (1) V/.sup.3 335.88 (2) Z 1 D.sub.c/g cm.sup.3 1.678 reflections collected 1919 unique reflections 102 R.sub.int 0.0684 R.sub.1 [I > 2(I)].sup.[a] 0.0648 wR.sub.2 [I > 2(I)].sup.[b] 0.1700 R.sub.1 (all data) 0.0649 wR.sub.2 (all data) 0.1702 GOF on F.sup.2 1.046 Completeness (data) 0.989 .sup.[a]R.sub.1 = F.sub.o| |F.sub.c/|F.sub.o|, .sup.[b]wR.sub.2 = {w[(F.sub.o).sup.2 (F.sub.c).sup.2].sup.2/w[(F.sub.o).sup.2].sup.2}.sup.1/2
Infrared Spectral Characterization of DAN-2:
(175) An infrared spectrum of DAN-2 is as shown in
(176) Thermal Stability Characterization of DAN-2:
(177) A thermogravimetric curve of DAN-2 is as shown in
(178) Differential Scanning Calorimeter (DSC) of DAN-2:
(179) A DSC curve of DAN-2 is as shown in
(180) Impact and Friction Sensitivity Characterization of DAN-2:
(181) According to a test method of a Federal Institute for Material Research and Testing (BAM), the impact sensitivity of DAN-2 is about 29 J, and the friction sensitivity is about 360 N.
Embodiment 11
(182) Synthesis and Test of (C.sub.6H.sub.14N.sub.2)[NH.sub.4(NO.sub.3).sub.3]
(183) Synthesis Method:
(184) 1) adding 2.0 mL of a nitric acid solution at a mass fraction of 65 percent into 0.78 mL of ammonia water at a mass fraction of 28 percent, and stirring the mixture at a normal temperature;
(185) 2) adding 1.14 g of 1,4-diazabicyclo[2.2.2]octane into a proper amount of water, and stirring the mixture at the normal temperature to dissolve the 1,4-diazabicyclo[2.2.2]octane;
(186) 3) mixing the solutions obtained in steps 1) and 2), stirring and filtering, washing residues with ethanol for three times, and performing vacuum drying on the washed residues to obtain a white powdery solid that is identified as hexagonal perovskite type compound (C.sub.6H.sub.14N.sub.2)[NH.sub.4(NO.sub.3).sub.3](No. DAN-4) with the yield of about 60 percent.
A Powder X-Ray Diffraction Identification Diagram:
(187) The powder X-ray diffraction diagram at the room temperature is as shown in
(188) TABLE-US-00017 TABLE 17 Characteristic peak values of powder X-ray diffraction of DAN-4 2/ d/ 10.3 8.60 17.7 5.02 20.4 4.35 23.9 3.72 24.8 3.58 27.0 3.30 29.7 3.00 30.5 2.93 32.2 2.78 37.0 2.43
Single-Crystal Structure Characterization Test:
(189) Detailed crystal test data are as shown in Table 18.
(190) TABLE-US-00018 TABLE 18 Single-crystal X-ray crystallographic data for DAN-4 Complex DAN-4 Formula C.sub.6H.sub.18N.sub.6O.sub.9 Formula weight 318.26 Temperature (K) 173 (2) Crystal system Hexagonal Space group P-62c a/ 10.0879 (1) c/ 7.1304 (1) V/.sup.3 628.41 (2) Z 2 D.sub.c/g cm.sup.3 1.682 reflections collected 10135 unique reflections 484 R.sub.int 0.0825 R.sub.1 [I > 2(I)].sup.[a] 0.0395 wR.sub.2 [I > 2(I)].sup.[b] 0.1235 R.sub.1 (all data) 0.0395 wR.sub.2 (all data) 0.1235 GOF on F.sup.2 1.211 Completeness (data) 1.000 .sup.[a]R.sub.1 = F.sub.o| |F.sub.c/|F.sub.o|, .sup.[b]wR.sub.2 = {w[(F.sub.o).sup.2 (F.sub.c).sup.2].sup.2/w[(F.sub.o).sup.2].sup.2}.sup.1/2
Thermal Stability Characterization of DAN-4:
(191) A thermogravimetric curve of DAN-4 is as shown in
(192) Differential Scanning Calorimeter (DSC) of DAN-4:
(193) A DSC curve of DAN-4 is as shown in
(194) The Amount of Gas Produced by DAN-4 Per Mole Number
(195) For judgment on products obtained by complete explosion of the energetic material in an oxygen-free environment, according to a document (J. Am. Chem. Soc. 2012, 134, 1422; J. Phys. Chem. A. 2014, 118, 4575; Chem. Eur. J. 2016, 22, 1141), final decomposition products include gaseous substances such as nitrogen and water, and solid substances such as elemental carbon (considering that oxygen atoms are preferentially combined with hydrogen atoms to form water). Therefore, 1 mole of DAN-4 may produce 12 moles of gas substances after complete explosion in the oxygen-free environment, with 6 moles of elemental carbon remaining. Under a condition that an enough amount of oxidant (such as commonly used NH.sub.4NO.sub.3) is mixed, DAN-4 per mole produces no solid residues after complete explosion. Particularly, without halogen elements, DAN-4 does not produce hydrogen halide gas after explosion, thereby reducing characteristic signals in actual application, and relieving environmental pollution.
(196) The perovskite-type energetic compound of the present application features high detonation heat, high energy density, high detonation velocity, high detonation pressure, high safety and extremely low impact, friction and electrostatic sensitivities, with non-volatile, non-decomposed and non-hygroscopic characteristics. The compound can be prepared in batches from cheap and readily-available raw materials through simple synthetic process which gives no by-products.
(197) The perovskite-type energetic compound of the present application can produce some effects which are unexpectable in the prior art when used as energetic materials such as explosives. Although perchlorate anion is an energetic ligand, most of the perchlorate-containing compounds at present cannot be used as practical energetic materials due to various disadvantages (see High Energy Materials: Propellants, Explosives and Pyrotechnics, p. 28, Jai Prakash Agrawal, Wiley-VCH Press, 2010). For example, common perchlorate salts such as sodium perchlorate and lithium perchlorate are highly hygroscopic in nature, and potassium perchlorate was used as a pro-oxidant for flash bombs, but later it was found to have excessive impact sensitivity and easy to explode during transportation. The theoretical detonation heat of ammonium perchlorate, which is still classified as an explosive, is only 1972 J/g, which is far below the detonation heat level of the energetic compound of the present application. However, even if the perovskite-type compound of the present application contains such explosive ligands, it can still maintain the excellent thermal stability and non-hygroscopic characteristic, which makes it an energetic material with high safety and easy storage. At the same time, due to the rich energetic ligands, the alternatively arranged oxidizing energetic anions and reducing organic cations in the space, high crystal density, powerful instantaneous burst capability, high energy density, and high detonation heat, detonation pressure and detonation velocity, the perovskite-type energetic compound, as explosives, has made a great leap in performance compared with the prior art.
(198) The above-mentioned embodiments are preferred implementation modes of the present application, but the implementation modes of the present application are not limited by the above-mentioned embodiments. Any other variations, modifications, replacements, combinations and simplifications that are made without departing from the spiritual essence and theory of the present application shall all be equivalent substitute modes and fall within the protection scope of the present application.