A modified 2,6-diamino-3,5-dinitropyrazine-1-oxide based hybrid energetic material with high decomposition rate, preparation method and application

Abstract

The application discloses a modified 2,6-diamino-3,5-dinitropyrazine-1-oxide-based hybrid energetic material with a high decomposition rate, a preparation method and application, and relates to the technical field of composite materials. The method first obtains an energetic high-nitrogen two-dimensional material (TAGP) formed by cross-linking of triaminoguanidine nitrate (TAGN) and an aldehyde solvent, and then uses the TAGP as a template material to induce LLM-105 to crystallize, so as to obtain an LLM-105 / TAGP composite energetic material through separation, washing and drying. The LLM-105-based composite energetic material provided by the application has the characteristics of a greatly improved thermal decomposition rate, and the decomposition rate is improved by 50% compared with that of LLM-105 raw materials, and the composite energetic material has high safety of LLM-105. The preparation process is mild, safe, environmentally friendly and easy to scale up, and is expected to be applied to the field of high-energy and safe propellant charges.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of composite materials, and particularly relates to a modified 2,6-diamino-3,5-dinitropyrazine-1-oxide-based hybrid energetic material with high decomposition rate, a preparation method and application thereof. BACKGROUND

[0002] As a new high-energy insensitive explosive, the crystal structure of 2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105) is in a wave-shaped layered accumulation, and there are a large number of intermolecular π-π conjugation and intramolecular hydrogen bond interactions. LLM-105 shows excellent safety to abnormal stimuli such as heat, static electricity, impact and friction. Its mechanical sensitivity and thermal sensitivity are close to that of “wood explosive” trisaminotrisnitrobenzene (TATB), and its detonation performance is better than that of TATB (US Patent, UCRL. JC. 142918, 2001; Annual Conference of ICT. Karlsrnhe, Germany, 2002; Journal of Physics: Conference Series 2478(3) 2023; Cryst Growth Des 23(9) 2023 6275-6289.). According to the public literature reports, the United States has been exploring the application of LLM-105 in the charge since 2000 (LLNL report UCRL-PRES-145524; LLNL report UCRL-CONF-212824), and the representative application field is the booster of W80 type of cruise missile (LLNL-TR-667207 CODT-2014-0933; LLNL-TR-668916 CODT-2014-0699; Science&Technology Review, LLNL, October-November 2018). However, the existing literature reports less about the energy release efficiency improvement of LLM-105 and the improvement range is limited, which brings certain challenges to the application of LLM-105-based explosives in the propellant field. Therefore, it is particularly important to develop an LLM-105-based composite energetic material with greatly improved energy release rate in the propellant field, which has application prospects.

[0003] The prior art uses ultrasonic-assisted microfluidic technology to prepare nano-LLM-105, and the thermal decomposition temperature of nano-LLM-105 is reduced by 2.11-5.69℃ compared with the raw material; and a preparation method of cubic short rod-shaped LLM-105 is disclosed, so that the thermal decomposition peak temperature of LLM-105 is advanced from 350℃ to 343℃. The decomposition rate of LLM-105 can also be controlled by adding a catalyst. Literature reports that adding Al / Ti amorphous alloy powder as a catalyst in LLM-105 reduces its thermal decomposition activation energy by 41.664 kJ / mol; and the field also uses ZIF-90 as a negative burning rate catalyst to make the thermal decomposition temperature of LLM-105 lag by 6.4℃, thereby improving its thermal stability. However, there are few studies on improving the decomposition rate of LLM-105 at present, and the improvement effect is limited. SUMMARY

[0004] In view of the deficiencies in the above background art, the present application provides a modified 2,6-diamino-3,5-dinitropyrazine-1-oxide-based hybrid energetic material with high decomposition rate, a preparation method and application. The present application crosslinks glyoxal (or glutaraldehyde) with triaminoguanidine nitrate (TAGN) to form a high-nitrogen two-dimensional material TAGP, uses TAGP as a hybrid material, induces LLM-105 to crystallize under its confinement, and realizes the growth of high-density LLM-105. The thermal decomposition rate of this product can be greatly improved.

[0005] The first object of the present application is to provide a preparation method of a modified 2,6-diamino-3,5-dinitropyrazine-1-oxide-based hybrid energetic material with high decomposition rate, comprising the following steps:

[0006] Dissolve triaminoguanidine nitrate in an organic solvent to obtain a triaminoguanidine nitrate solution;

[0007] Add LLM-105 to the triaminoguanidine nitrate solution, mix uniformly, then add an aldehyde solvent, and react at 140-150℃ for 1-2 hours to obtain a reaction solution;

[0008] Add an anti-solvent to the reaction solution to precipitate a solid product, thereby obtaining a modified 2,6-diamino-3,5-dinitropyrazine-1-oxide-based hybrid energetic material with high decomposition rate.

[0009] Preferably, the mass fraction of triaminoguanidine nitrate in LLM-105 is 0.5-5%.

[0010] Preferably, the molar ratio of triaminoguanidine nitrate to the aldehyde solvent is 1:2-6.

[0011] Preferably, the organic solvent is dimethyl sulfoxide; and the aldehyde solvent is glyoxal or glutaraldehyde.

[0012] Preferably, the triaminoguanidine nitrate solution is prepared by adding triaminoguanidine nitrate into an organic solvent, stirring at 140-150 DEG C for 15-30 minutes to completely dissolve.

[0013] Preferably, the temperature of the reaction solution is set to 25-100 DEG C when the anti-solvent is added, and the anti-solvent is deionized water or ethanol.

[0014] Preferably, the dropping speed of the anti-solvent is 0.5-10 mL / min.

[0015] Preferably, after the solid product is precipitated, the high-decomposition-rate modified 2,6-diamino-3,5-dinitropyrazine-1-oxide-based hybrid energetic material is obtained by suction filtration and drying.

[0016] The second object of the present application is to provide a high-decomposition-rate modified 2,6-diamino-3,5-dinitropyrazine-1-oxide-based hybrid energetic material.

[0017] The third object of the present application is to provide an application of the high-decomposition-rate modified 2,6-diamino-3,5-dinitropyrazine-1-oxide-based hybrid energetic material in high-energy safe propellant charges.

[0018] Compared with the prior art, the present application has the following beneficial effects:

[0019] The present application provides a high-decomposition-rate modified 2,6-diamino-3,5-dinitropyrazine-1-oxide-based hybrid energetic material, a preparation method and an application. The present application obtains a two-dimensional high-nitrogen material by cross-linking TAGN and glyoxal, and grows LLM-105 under the limited constraint of the two-dimensional high-nitrogen material to obtain qy-LLM-105. The LLM-105-based composite energetic material provided by the present application has the characteristics of a significantly improved thermal decomposition rate, and the decomposition rate is improved by 50% compared with the LLM-105 raw material, and the composite energetic material also has the high safety of LLM-105. The present application mainly shortens the reaction process of qy-LLM-105 decomposition under the catalysis of the two-dimensional material TAGP, so as to improve the decomposition rate and have a lower activation energy. The preparation process involved in the present application has mild conditions, is safe and environmentally friendly, and is easy to scale up, and is expected to be applied in the field of high-energy safe propellant charges.

[0020] The present application provides a high-decomposition-rate modified 2,6-diamino-3,5-dinitropyrazine-1-oxide-based hybrid energetic material, a preparation method and an application. The present application obtains a two-dimensional high-nitrogen material by cross-linking TAGN and glyoxal, and grows LLM-105 under the limited constraint of the two-dimensional high-nitrogen material to obtain qy-LLM-105. The LLM-105-based composite energetic material provided by the present application has the characteristics of a significantly improved thermal decomposition rate, and the decomposition rate is improved by 50% compared with the LLM-105 raw material, and the composite energetic material also has the high safety of LLM-105. The present application mainly shortens the reaction process of qy-LLM-105 decomposition under the catalysis of the two-dimensional material TAGP, so as to improve the decomposition rate and have a lower activation energy. The preparation process involved in the present application has mild conditions, is safe and environmentally friendly, and is easy to scale up, and is expected to be applied in the field of high-energy safe propellant charges.

[0020] The process is simple, and the raw material cost is low, which can greatly improve the decomposition rate of LLM-105 on one hand, and can improve the density of LLM-105 on the other hand. By adjusting the process conditions, products with different reaction activities can be obtained. Since TAGP itself contains energy, the decomposition rate of LLM-105 can be adjusted under the premise of maintaining the original energy level of LLM-105. The present application provides a new technical approach for adjusting the decomposition rate of energetic materials. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 Scanning electron microscope images of high-decomposition-rate LLM-105-based hybrid energetic materials prepared for Examples 1-6.

[0022] Figure 2 X-ray diffraction patterns of high-decomposition-rate LLM-105-based hybrid energetic materials prepared for Examples 1-6.

[0023] Figure 3 DSC analysis graphs of high-decomposition-rate LLM-105-based hybrid energetic materials prepared for Examples 1-6. DETAILED DESCRIPTION

[0024] In order for those skilled in the art to better understand the technical solutions of the present application and to implement them, the present application will be further described below in conjunction with specific embodiments and drawings, but the embodiments are not limiting on the present application.

[0025] The present application aims at the difficulty in greatly improving the thermal decomposition rate of LLM-105 in the prior art, and discloses a LLM-105-based composite energetic material with fast decomposition characteristics and a preparation method thereof. By introducing an energetic catalyst, the thermal decomposition rate of LLM-105 is significantly improved. The reaction condition is mild, safe, environmentally friendly, and easy to scale up. Meanwhile, the composite material takes into account the high safety of LLM-105, and has a good application prospect in the field of high-energy safe propellant charges.

[0026] In order to achieve the above-mentioned purpose, the first aspect of the present application provides a preparation method of a high-decomposition-rate modified 2,6-diamino-3,5-dinitropyrazine-1-oxide-based hybrid energetic material (LLM-105-based hybrid energetic material), comprising the following steps:

[0027] Dissolve triaminoguanidine nitrate in an organic solvent to obtain a triaminoguanidine nitric acid solution;

[0028] Add LLM-105 to the triaminoguanidine nitric acid solution, mix uniformly, then add an aldehyde solvent, and react at 140-150℃ for 1-2 hours to obtain a reaction solution;

[0029] The reaction solution is added with an anti-solvent, and a solid product is precipitated, to obtain the modified 2,6-diamino-3,5-dinitropyrazine-1-oxide-based hybrid energetic material with high decomposition rate.

[0030] The present application firstly obtains an energetic high-nitrogen two-dimensional material (TAGP) formed by cross-linking triaminoguanidine nitrate (TAGN) and an aldehyde solvent, then uses the TAGP as a template material to induce LLM-105 to crystallize, and finally obtains an LLM-105 / TAGP composite energetic material through separation, washing and drying. The LLM-105-based composite energetic material provided by the present application has the characteristics of a greatly improved thermal decomposition rate, and the decomposition rate is improved by 50% compared with the LLM-105 raw material. Meanwhile, the composite energetic material has the high safety of LLM-105. The preparation process involved in the present application has the advantages of mild conditions, safety and environmental protection, and easy scaling up, and is expected to be applied to the field of high-energy and safe propellant charges.

[0031] The mass fraction of the triaminoguanidine nitrate in the LLM-105 is 0.5-5%.

[0032] The molar ratio of the triaminoguanidine nitrate to the aldehyde solvent is 1:2-6.

[0033] The organic solvent is dimethyl sulfoxide, and the aldehyde solvent is glyoxal or glutaraldehyde.

[0034] The triaminoguanidine nitrate solution is prepared by adding triaminoguanidine nitrate into an organic solvent, stirring at 140-150℃ for 15-30 minutes, and completely dissolving the triaminoguanidine nitrate.

[0035] The temperature of the reaction solution is set to 25-100℃ when the anti-solvent is added, and the anti-solvent is deionized water or ethanol.

[0036] The dropwise adding speed of the anti-solvent is 0.5-10 mL / min.

[0037] After the solid product is precipitated, the high-decomposition-rate modified 2,6-diamino-3,5-dinitropyrazine-1-oxide-based hybrid energetic material is obtained through suction filtration and drying.

[0038] In an embodiment, a preparation method of a high-decomposition-rate LLM-105-based hybrid energetic material is characterized by the following steps:

[0039] Step 1: adding TAGN into a dimethyl sulfoxide (DMSO) solution, stirring at 140-150℃ for 20 minutes, and completely dissolving the TAGN;

[0040] Step 2: adding LLM-105 into the solution prepared in step 1, continuously stirring for 30 minutes, and completely dissolving the LLM-105;

[0041] Step 3: add glyoxal or glutaraldehyde into the solution prepared in step 2, and react at 140-150℃ for 1 hour;

[0042] Step 4: add anti-solvent dropwise into the solution prepared in step 3 to precipitate solid product;

[0043] Step 5: perform suction filtration and drying on the solid product obtained in step 4 to obtain LLM-105-based composite energetic material (qy-LLM-105).

[0044] The mass fraction of TAGN in step 2 is 0.5%-5%. The molar ratio of glyoxal (or glutaraldehyde) to TAGN in step 3 is 1:1-6:1. The solution is kept at 25℃-100℃ when the anti-solvent is added dropwise in step 4. The anti-solvent added in step 4 is one of deionized water, methanol and ethanol. The dropwise addition rate of the anti-solvent in step 4 is 0.5 mL / min-10 mL / min.

[0045] The second aspect of the present application provides a high-decomposition-rate modified 2,6-diamino-3,5-dinitropyrazine-1-oxide-based hybrid energetic material.

[0046] The third aspect of the present application provides application of a high-decomposition-rate modified 2,6-diamino-3,5-dinitropyrazine-1-oxide-based hybrid energetic material in high-energy safe propellant charge.

[0047] It should be noted that the experimental methods used in the present application are conventional methods unless otherwise specified; the reagents and materials used are commercially available unless otherwise specified.

[0048] Example 1

[0049] A preparation method of a high-decomposition-rate LLM-105-based hybrid energetic material includes the following process steps:

[0050] TAGN dissolution: 0.08 g of TAGN is weighed and added to 30 mL of DMSO, and heated to 140℃ in an oil bath, and stirred for 20 min until the TAGN is completely dissolved.

[0051] LLM-105 dissolution: 2.925 g of LLM-105 (2.5% of the mass fraction of TAGN) is weighed and added to the dissolved TAGN solution, and continuously stirred for 30 min until it is completely dissolved to obtain a TAGN / LLM-105 solution;

[0052] Preparation of high-nitrogen two-dimensional material: 0.10 mL of glyoxal (molar ratio of glyoxal to TAGN is 4:1) was added to the dissolved TAGN / LLM-105 solution, and stirred at 140°C for 1 h to generate the high-nitrogen two-dimensional material.

[0053] Crystallization of qy-LLM-105: the solution was kept at 100°C, and 90°C deionized water was added at a rate of 6 mL / min by peristaltic pump to precipitate the solid product.

[0054] Collection of the product: the product was washed with deionized water, and after suction filtration and vacuum freeze-drying, a yellow powder of qy-LLM-105 was obtained.

[0055] The qy-LLM-105 prepared in Example 1 was subjected to scanning electron microscope analysis, as shown in Figure 1 , the crystal morphology was interpenetrating prismatic.

[0056] The qy-LLM-105 prepared in Example 1 was subjected to XRD analysis, as shown in Figure 2 , compared with the original LLM-105, the diffraction peak intensity of Example 1 at 11.2° and 33.9° was significantly reduced, and the diffraction peak intensity at 22.4° was significantly enhanced.

[0057] The qy-LLM-105 prepared in Example 1 was subjected to vacuum density analysis (gas displacement method), and the density test result was 1.9282 g / cm 3 .

[0058] The qy-LLM-105 prepared in Example 1 was subjected to DSC analysis, and the results are shown in Figure 3 .

[0059] The qy-LLM-105 prepared in Example 1 was subjected to activation energy calculation, and the results are shown in Table 1. The activation energy is lower than that of the original LLM-105, indicating a faster reaction rate.

[0060] Example 2

[0061] A preparation method of a high-decomposition-rate LLM-105-based hybrid energetic material, comprising the following process steps:

[0062] Dissolution of TAGN: 0.02 g of TAGN was weighed into 30 mL of DMSO, and heated to 140°C in an oil bath, and stirred for 20 min until the TAGN was completely dissolved.

[0063] Dissolution of LLM-105: 2.985 g of LLM-105 (mass fraction of TAGN is 0.5%) was weighed and added into the dissolved TAGN solution, and stirred for 30 min to completely dissolve, to obtain a TAGN / LLM-105 solution;

[0064] Preparation of high-nitrogen two-dimensional material: 0.007 mL of glyoxal (molar ratio of glyoxal to TAGN is 1:1) was weighed and added into the dissolved TAGN / LLM-105 solution, and stirred at 140°C for 1 h to generate a high-nitrogen two-dimensional material.

[0065] Crystallization of qy-LLM-105: the solution was kept at 100°C, and 90°C deionized water was added at a rate of 6 mL / min by using a peristaltic pump to precipitate solid products.

[0066] Collection of products: the products were washed with deionized water, and after being filtered and vacuum freeze-dried, qy-LLM-105 in the form of a bright yellow powder was obtained.

[0067] The qy-LLM-105 prepared in Example 2 was subjected to scanning electron microscope analysis, as shown in FIG. 2, and the crystal morphology thereof was in the form of interlaced prisms. Figure 1

[0068] The qy-LLM-105 prepared in Example 2 was subjected to XRD analysis, as shown in FIG. 3. Figure 2 Compared with the original LLM-105, the diffraction peak intensity of Example 2 at 11.2° and 33.9° was significantly reduced, and the diffraction peak intensity at 22.4° was significantly enhanced.

[0069] The qy-LLM-105 prepared in Example 2 was subjected to vacuum density analysis (gas displacement method), and the density test result thereof was 1.9176 g / cm 3 , and the density improvement effect was not significant enough.

[0070] The qy-LLM-105 prepared in Example 2 was subjected to DSC analysis, and the result is shown in FIG. 4. Figure 3

[0071] The qy-LLM-105 prepared in Example 2 was subjected to activation energy calculation, and the result is shown in Table 1. The activation energy thereof was lower than that of the original LLM-105, indicating that the reaction rate was faster.

[0072] Example 3

[0073] A preparation method of a high-decomposition-rate LLM-105-based hybrid energetic material, comprising the following process steps:

[0074] ​​Dissolving TAGN: Weigh 0.15 g of TAGN and add it to 30 mL of DMSO. Heat the mixture in an oil bath to 140°C and stir for 20 min until the TAGN is completely dissolved.

[0075] Dissolution of LLM-105: Weigh 2.85 g of LLM-105 (TAGN mass fraction is 5%) and add it to the dissolved TAGN solution. Stir continuously for 30 min until it is completely dissolved to obtain TAGN / LLM-105 solution.

[0076] Generation of high-nitrogen two-dimensional materials: 0.31 mL of glyoxal (molar ratio of glyoxal to TAGN is 6:1) was added to the dissolved TAGN / LLM-105 solution and stirred at 140℃ for 1 h to generate high-nitrogen two-dimensional materials.

[0077] Crystallization of qy-LLM-105: The solution was kept at 100℃, and deionized water at 90℃ was added at a rate of 6 mL / min using a peristaltic pump to precipitate a solid product.

[0078] Product collection: The product was washed with deionized water, filtered, and freeze-dried under vacuum to obtain a bright yellow powder, qy-LLM-105.

[0079] The qy-LLM-105 prepared in Example 3 was analyzed by scanning electron microscopy, such as... Figure 1 As shown, its crystal structure is prismatic, and the aggregation phenomenon is obvious.

[0080] XRD analysis was performed on qy-LLM-105 prepared in Example 3, as follows: Figure 2 As shown, compared with the original LLM-105, the diffraction peak intensity of Example 3 is significantly reduced at 11.2° and 33.9°, while the diffraction peak intensity at 22.4° is significantly enhanced.

[0081] Vacuum density analysis (gas displacement method) was performed on qy-LLM-105 prepared in Example 3, and the density test result was 1.9577 g / cm³. 3 It is slightly lower than that of Example 5.

[0082] The qy-LLM-105 prepared in Example 3 was analyzed by DSC, and the results are as follows: Figure 3 As shown.

[0083] The activation energy of qy-LLM-105 prepared in Example 3 was calculated, and the results are shown in Table 1. Its activation energy was significantly lower than that of the original LLM-105, indicating that the reaction rate was faster.

[0084] Elemental analysis was performed on Example 3, and the results are shown in Table 2.

[0085] The combustion heat test of Example 3 was carried out, and the result was 9.61 kJ / g, and the calculated enthalpy of formation was -10.31 kJ / mol.

[0086] Example 4

[0087] A preparation method of a high-decomposition-rate LLM-105-based hybrid energetic material, comprising the following process steps:

[0088] Dissolution of TAGN: 0.15 g of TAGN was weighed and added to 30 mL of DMSO, and heated to 150℃ in an oil bath, and stirred for 20 min until the TAGN was completely dissolved.

[0089] Dissolution of LLM-105: 2.85 g of LLM-105 (5% by mass fraction of TAGN) was weighed and added to the dissolved TAGN solution, and continuously stirred for 30 min until it was completely dissolved, to obtain a TAGN / LLM-105 solution;

[0090] Generation of high-nitrogen two-dimensional material: 0.21 mL of glyoxal (molar ratio of glyoxal to TAGN was 4:1) was measured and added to the dissolved TAGN / LLM-105 solution, and stirred at 150℃ for 1 h to generate a high-nitrogen two-dimensional material.

[0091] Crystallization of qy-LLM-105: the solution was kept at 100℃, and 90℃ deionized water was added at a rate of 6 mL / min through a peristaltic pump to precipitate the solid product.

[0092] Collection of product: the product was washed with deionized water, and after suction filtration and vacuum freeze-drying, a brownish yellow powder of qy-LLM-105 was obtained.

[0093] The qy-LLM-105 prepared in Example 4 was subjected to scanning electron microscope analysis, as shown in Figure 1 , and the crystal structure was prismatic with agglomeration.

[0094] The qy-LLM-105 prepared in Example 4 was subjected to XRD analysis, as shown in Figure 2 , compared with the original LLM-105, the diffraction peak intensity of Example 4 at 11.2° and 33.9° was significantly reduced, and the diffraction peak intensity at 22.4° was significantly enhanced.

[0095] The qy-LLM-105 prepared in Example 4 was subjected to vacuum density analysis (gas displacement method), and the density test result was 1.9465 g / cm 3 .

[0096] The qy-LLM-105 prepared in Example 4 was subjected to DSC analysis, and the result is shown in Figure 3 .

[0097] The activation energy of qy-LLM-105 prepared in Example 4 was calculated, and the results are shown in Table 1. Its activation energy was significantly lower than that of the original LLM-105, indicating that the reaction rate was faster.

[0098] Example 5

[0099] A method for preparing an LLM-105-based hybrid energetic material with a high decomposition rate includes the following process steps:

[0100] Dissolving TAGN: Weigh 0.15 g of TAGN and add it to 30 mL of DMSO. Heat the mixture in an oil bath to 140°C and stir for 20 min until the TAGN is completely dissolved.

[0101] Dissolution of LLM-105: Weigh 2.85 g of LLM-105 (TAGN mass fraction is 5%) and add it to the dissolved TAGN solution. Stir continuously for 30 min until it is completely dissolved to obtain TAGN / LLM-105 solution.

[0102] Generation of high-nitrogen two-dimensional materials: 0.18 mL of glutaraldehyde (molar ratio of glutaraldehyde to TAGN is 2:1) was added to the dissolved TAGN / LLM-105 solution and stirred at 140℃ for 1 h to generate high-nitrogen two-dimensional materials.

[0103] Crystallization of qy-LLM-105: The solution was kept at 100℃, and deionized water at 25℃ was added at a rate of 6 mL / min using a peristaltic pump to precipitate a solid product.

[0104] Product collection: The product was washed with deionized water, filtered, and freeze-dried under vacuum to obtain a bright yellow powder, qy-LLM-105.

[0105] The qy-LLM-105 prepared in Example 5 was analyzed by scanning electron microscopy, such as... Figure 1 As shown, its crystal structure is prismatic and exhibits aggregation.

[0106] XRD analysis was performed on qy-LLM-105 prepared in Example 5, as follows: Figure 2 As shown, compared with the original LLM-105, the diffraction peak intensity of Example 5 is significantly reduced at 11.2° and 33.9°, while the diffraction peak intensity at 22.4° is significantly enhanced.

[0107] Vacuum density analysis (gas displacement method) was performed on qy-LLM-105 prepared in Example 5, and the density test result was 1.9385 g / cm³. 3The density of LLM-105 is improved by TAGN-glutaraldehyde crosslinking agent, which is lower than that of TAGN-glyoxal crosslinking agent.

[0108] The qy-LLM-105 prepared in Example 5 was subjected to DSC analysis, and the results are shown in Figure 3 .

[0109] The qy-LLM-105 prepared in Example 5 was subjected to activation energy calculation, and the results are shown in Table 1. The activation energy of qy-LLM-105 is greatly reduced compared with that of original LLM-105, indicating that the reaction rate is faster.

[0110] Example 6

[0111] A preparation method of a high-decomposition-rate LLM-105-based hybrid energetic material, comprising the following process steps:

[0112] Dissolution of TAGN: 0.15 g of TAGN was weighed and added to 30 mL of DMSO, and heated to 140°C in an oil bath, and stirred for 20 min until the TAGN was completely dissolved.

[0113] Dissolution of LLM-105: 2.85 g of LLM-105 (5% by mass of TAGN) was weighed and added to the dissolved TAGN solution, and stirred for 30 min until it was completely dissolved, to obtain a TAGN / LLM-105 solution;

[0114] Generation of high-nitrogen two-dimensional material: 0.10 mL of glyoxal (molar ratio of glyoxal to TAGN is 2:1) was measured and added to the dissolved TAGN / LLM-105 solution, and stirred at 140°C for 1 h to generate a high-nitrogen two-dimensional material.

[0115] Crystallization of qy-LLM-105: the solution was kept at 100°C, and 25°C ethanol was added at a rate of 6 mL / min through a peristaltic pump to precipitate the solid product.

[0116] Collection of product: the product was washed with deionized water, and after suction filtration and vacuum freeze-drying, qy-LLM-105 in the form of a bright yellow powder was obtained.

[0117] The qy-LLM-105 prepared in Example 6 was subjected to scanning electron microscope analysis, and the results are shown in Figure 1 , which has a prismatic crystal structure with a large aspect ratio, and ethanol has a good dispersion effect on the crystals.

[0118] The qy-LLM-105 prepared in Example 6 was subjected to XRD analysis, and the results are shown in Figure 2As shown, compared with the original LLM-105, the diffraction peak intensity of Example 6 at 11.2° and 33.9° is significantly reduced, and the diffraction peak intensity at 22.4° is significantly enhanced.

[0119] The qy-LLM-105 prepared in Example 6 was subjected to vacuum density analysis (gas displacement method), and the density test result was 1.9755 g / cm 3 Compared with Example 9, there is an increase, which indicates that using ethanol as an anti-solvent can better improve the density.

[0120] The qy-LLM-105 prepared in Example 6 was subjected to DSC analysis, and the result is shown in Figure 3

[0121] The qy-LLM-105 prepared in Example 6 was subjected to activation energy calculation, and the result is shown in Table 1. The activation energy is significantly reduced compared with the original LLM-105, indicating that the reaction rate is faster.

[0122] Table 1 is the activation energy calculation result of the high-decomposition-rate LLM-105-based hybrid energetic material prepared in Examples 1-6.

[0123]

[0124] Table 2 is the elemental analysis result of the high-decomposition-rate LLM-105-based hybrid energetic material prepared in Example 3.

[0125]

[0126] The preferred embodiments and their effects are described in the present application. However, once the basic creative concept is known, those skilled in the art can make additional changes and modifications to the embodiments. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications falling within the scope of the present application.

[0127] Although the embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made thereto without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.​

Claims

1. A method for preparing a high-decomposition-rate modified 2,6-diamino-3,5-dinitropyrazine-1-oxide-based hybrid energetic material, characterized in that, Includes the following steps: Triaminoguanidine nitrate is dissolved in an organic solvent to obtain a triaminoguanidine nitrate solution; LLM-105 was added to a triaminoguanidine nitric acid solution, mixed thoroughly, and then an aldehyde solvent was added. The mixture was reacted at 140-150°C for 1-2 hours to obtain a reaction solution. Adding an antisolvent to the reaction solution precipitates a solid product, thus obtaining a modified 2,6-diamino-3,5-dinitropyrazine-1-oxide-based hybrid energetic material with a high decomposition rate. The triaminoguanidine nitrate constitutes 0.5-5% of the mass of LLM-105; The molar ratio of the triaminoguanidine nitrate to the aldehyde solvent is 1:2~6; The organic solvent is dimethyl sulfoxide; the aldehyde solvent is glyoxal or glutaraldehyde; The triaminoguanidine nitric acid solution is prepared by adding triaminoguanidine nitrate to an organic solvent and stirring at 140-150°C for 15-30 minutes until it is completely dissolved. When adding the antisolvent, the reaction solution temperature is set to 25~100℃, where the antisolvent is deionized water or ethanol; The dropping rate of the antisolvent is 0.5 ~ 10 mL / min; After the solid product is precipitated, it is filtered and dried to obtain a modified 2,6-diamino-3,5-dinitropyrazine-1-oxide-based hybrid energetic material with a high decomposition rate.

2. A modified 2,6-diamino-3,5-dinitropyrazine-1-oxide-based hybrid energetic material with a high decomposition rate prepared by the method of claim 1.

3. The application of the modified 2,6-diamino-3,5-dinitropyrazine-1-oxide-based hybrid energetic material with high decomposition rate as described in claim 2 in high-energy safe propellant loading.

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