CN109053620B - DNTF with low shock wave sensitivity and preparation method thereof - Google Patents
DNTF with low shock wave sensitivity and preparation method thereof Download PDFInfo
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- CN109053620B CN109053620B CN201811031142.9A CN201811031142A CN109053620B CN 109053620 B CN109053620 B CN 109053620B CN 201811031142 A CN201811031142 A CN 201811031142A CN 109053620 B CN109053620 B CN 109053620B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/08—1,2,5-Oxadiazoles; Hydrogenated 1,2,5-oxadiazoles
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Abstract
The application provides a DNTF with low shock wave sensitivity and a preparation method thereof. The mass percentage of the solvent used in the method to the DNTF crude product is 4:1, stirring and heating are carried out at 500r/m, and the DNTF is stirred for 20min at the temperature of 80-85 ℃; adding 1% crystal form control agent, stirring at 80-85 deg.C 1000r/m for 10 min; when the stirring speed is reduced to 800r/m, naturally cooling; stirring for 10min at the temperature of 63.5-64 ℃; controlling the temperature, increasing the stirring speed to 1000r/m, dripping deionized water at the speed of 0.8ml/min, and diluting the DNTF solution for 60-90 min; stopping stirring, carrying out suction filtration, washing and drying to obtain the DNTF crystal with low shock wave sensitivity. The DNTF crystal prepared by the recrystallization process method overcomes the defect of high DNTF shock wave sensitivity in the background technology.
Description
Technical Field
The invention relates to a recrystallization process method for preparing DNTF elementary explosive with low shock wave sensitivity, belonging to the field of explosive synthesis.
Background
3, 4-dinitrofurazan-based furoxan (DNTF) is used as a high-performance third-generation explosive, and compared with the performance of second-generation explosives such as hexogen, octogen and the like, the 3, 4-dinitrofurazan-based furoxan (DNTF) has higher density, detonation velocity and detonation heat, and the detonation performance is obviously superior to that of octogen (HMX) and hexogen (RDX) and is close to CL-20. A research on the performance and application of a high-energy density material 3, 4-dinitrofurazan-based furoxan (the report of war engineering, No. 2 in 2004, P155-158) discloses a DNTF elementary explosive, acetic acid is mainly used as a solvent, water is used as a non-solvent to recrystallize DNTF, and the impact sensitivity of the recrystallized DNTF is high (96%), but the shock wave sensitivity is not reported. Research on the sensitivity of DNTF-based insensitive explosion-inducing medicine to shock waves and the small-size explosion-inducing performance (initiating explosive devices, No. 6 of 2011, P22-25) indicates that DNTF is sensitive to shock waves and has two methods for reducing the sensitivity of the shock waves, namely, the crystal quality is improved, and substances with low impact sensitivity are mixed. Patent ZL201510100531.2 'a high-quality single-substance explosive recrystallization method' discloses that a mixed explosive prepared by taking high-quality DNTF as a main explosive has high forming density and low mechanical sensitivity, but does not relate to the shock wave sensitivity of DNTF.
Disclosure of Invention
In order to overcome the defects in the background art, the invention provides a recrystallization process of a DNTF explosive with low shock wave sensitivity.
The invention provides a recrystallization method for preparing DNTF explosive with low shock wave sensitivity, which comprises the following steps:
(1) adding a solvent concentrated sulfuric acid and a DNTF crude product into a 1000mL flask according to the mass ratio of 4:1, heating to 80-85 ℃ in a water bath, mechanically stirring at the speed of 500r/m for 20 min;
(2) adding Calcium Stearate (CS) or sodium dodecyl sulfate (DBS) accounting for 1 percent of the mass of the DNTF crude product, and continuously stirring for 10min at the temperature of 80-85 ℃, wherein the stirring speed is 1000 r/m;
(3) stopping heating, reducing the stirring speed to 800r/m, naturally cooling at the room temperature of 20-25 ℃, and keeping the temperature and stirring for 10min at the temperature of 63.5-64 ℃;
(4) strictly controlling the temperature, increasing the stirring speed to 1000r/m, dripping non-solvent deionized water at the dilution speed of 0.8ml/min to slowly separate out DNTF in the solution, precipitating the DNTF to the surface of a DNTF crystal nucleus to slowly grow, and diluting and stirring for 60-90 min;
(5) stopping dripping the non-solvent deionized water, stopping stirring, pouring the suspension in the flask into a sand core funnel paved with filter paper, carrying out suction filtration and water washing for three times, and drying to obtain the DNTF with low shock wave sensitivity.
(6) Weighing the DNTF with low shock wave sensitivity, adding the DNTF into a bonding and curing system, and mixing, wherein the mass ratio of the DNTF with low shock wave sensitivity to the bonding and curing system is 9: 1. The powder is charged according to the requirement of a small partition plate test of method 101 of GJB2178A-2005 booster safety test method, and the thickness value (G) of the 50 percent partition plate is used50Mm) characterizes the shock wave sensitivity.
The bonding and curing system in the step (6) is hydroxyl-terminated polybutadiene (HTPB)/toluene-2, 4-diisocyanate (TDI), and the mass ratio of the hydroxyl-terminated polybutadiene to the toluene-2, 4-diisocyanate is 1000: 1.
the invention has the characteristics that: the solvent-non-solvent recrystallization process adopted by the invention has several characteristics.
The technological approach for reducing DNTF shock wave sensitivity is to improve the crystal quality, the realized technological approach is to control the slow generation of crystal nuclei and the slow growth of crystals, the technological parameters comprise stirring speed, heat preservation temperature, heat preservation time, dilution speed and the like based on the principle, and the internal quality of the crystals and shock wave sensitivity data of the obtained product are finally determined through comparison and analysis through repeated recrystallization tests.
Using higher solubility and higher boiling polar solvent concentrated H2SO4The DNTF solution can be fully dissolved, the concentration of DNTF solution can be increased, the dosage of recrystallization solvent can be reduced, the crystallization point can be caused to appear at a higher temperature, and the control of the number of crystal nuclei is facilitated; the mass ratio of solvent to crude DNTF and the heating temperature are determined by the solubility of DNTF in combination with the concentration of the solution obtained from the experimental investigation suitable for the solvent-nonsolvent recrystallization process. The use of the crystal form control agent Calcium Stearate (CS) or sodium dodecyl sulfate (DBS) can improve the internal quality and external appearance of crystal grains in the crystal growth process; the crystal nucleus quality can be improved by naturally cooling and slowly crystallizing at room temperature environment and preserving heat at a crystallization point, and the determined crystallization point and the heat preservation time can be obtained through multiple tests. Therefore, the recrystallization process method can effectively reduce the shock wave sensitivity of the DNTF explosive and improve the safety.
GJB2178A-2005 method 101 Small partition test, method for testing safety of booster drugs. Test according to BrCarrying out a program of a uceton method, wherein the lifting step length of the thickness of the partition plate is 0.2 mm; the zero clearance average burst depth is the average of the 5-shot test burst depths when the measured charge is directly detonated by the main charge. The shock wave sensitivity of the tested sample is judged according to the depth of the explosion mark on the steel identification block at the tail end of the tested sample, if the depth of the explosion mark is more than 50 percent of the average depth of the explosion mark when the gap is zero (the thickness of the partition plate is 0), the test sample is judged to be detonated, and if not, the test sample is judged to be failed to detonate. Calculate fifty percent explosive partition mean G as GJB37750The/mm characterizes the shock wave sensitivity of the test specimen.
And (3) preparing a mixed explosive with the same formula according to the step (6) by respectively adopting the existing DNTF crude product and the DNTF with low shock wave sensitivity obtained by the application, and testing the shock wave sensitivity according to the method. DNTF mixed explosive G measured by the application50Up to 12.29mm, G determined from the crude DNTF of the prior art50A reduction of 39.6% for 20.36 mm.
Detailed Description
The present invention will be described in further detail by way of examples.
Example 1
This example was carried out with reference to the following weight percent compositions: 99.5% of crude DNTF, 98% of concentrated sulfuric acid and 1% of calcium stearate. The preparation method of this example is as follows:
the hectogram-level preparation process comprises the following steps:
(1) DNTF solubilization
100g of crude DNTF and 400g of 98% concentrated sulfuric acid are weighed and placed in a 1000mL flask, the mechanical stirring speed is started to 500r/m, the mixture is heated in a water bath to 80-85 ℃, and the mixture is stirred for 20min at the temperature.
(2) DNTF morphology control
Adding 1gCS, and continuing stirring for 10min at 80-85 ℃ with the stirring speed of 1000 r/m;
(3) DNTF Crystal precipitation
Stopping heating, reducing the stirring speed to 800r/m, naturally cooling at the room temperature of 20-25 ℃, and preserving the heat for 10min when the temperature is 63.5-64 ℃; strictly controlling the crystallization point temperature, increasing the stirring speed to 1000r/m, and dripping non-solvent deionized water at the dilution speed of 0.8ml/min to slowly precipitate DNTF in the solution, wherein DNTF crystal nuclei grow slowly, and the dilution and stirring time is 60-90 min;
(4) DNTF recrystallization sample acquisition
Stopping stirring, carrying out suction filtration and water washing for three times, and drying to obtain the DNTF with low shock wave sensitivity.
(5) DNTF shock wave sensitivity test sample preparation
Weighing a certain mass of recrystallized DNTF and hydroxyl-terminated polybutadiene (HTPB)/toluene-2, 4-diisocyanate (TDI) system (the mass ratio is 1000: 1), mechanically stirring and mixing (the ratio of the two is 90:10), and simultaneously preparing the same formula based on crude DNTF. According to the requirements of GJB2178A-2005 method 101, the sample is cast into a mold with an inner diameter of 5.1mm, an outer diameter of 25mm and a height of 50mm, and after complete curing, the sample is prepared, and the two are tested for shock wave sensitivity and compared.
Example 2
This example was carried out with reference to the following weight percent compositions: 99.5 percent of DNTF crude product, and a solvent of 98 percent of concentrated sulfuric acid and 1 percent of sodium dodecyl sulfate. The preparation process of this example refers to example 1.
Table 1 example performance data
As can be seen from the table above, the DNTF elementary explosive with low shock wave sensitivity prepared by the method has reduced and uniform granularity and slightly improved density. Compared with the prior art, the shock wave sensitivity of the mixed explosive based on the DNTF single-substance explosive is obviously reduced, the safety is improved, and the forming density is improved.
Claims (1)
1. A recrystallization process for preparing DNTF with low shock wave sensitivity is characterized by comprising the following steps:
(1) adding 98% concentrated sulfuric acid and a DNTF crude product into a 1000mL flask, heating to 80-85 ℃ in a water bath, mechanically stirring at a speed of 500r/m for 20 min;
(2) adding a crystal form control agent accounting for 1% of the mass of the DNTF crude product, wherein the crystal form control agent is Calcium Stearate (CS) or sodium dodecyl sulfate (DBS), and stirring for 10min at the temperature of 80-85 ℃, and the stirring speed is 1000 r/m;
(3) stopping heating, reducing the stirring speed to 800r/m, naturally cooling to 63.5-64 ℃, and preserving heat for 10 min;
(4) increasing the stirring speed to 1000r/m, and dripping deionized water at the dilution speed of 0.8ml/min, wherein the dilution and stirring time is 60-90 min;
(5) stopping stirring, carrying out suction filtration, washing with water, and drying to obtain the DNTF with low shock wave sensitivity; the mass ratio of the 98% concentrated sulfuric acid to the DNTF crude product in the step (1) is 4: 1.
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