NH-SiGO / ADN / GAP-ETPE composite, preparation method and application

Abstract

This invention provides an NH-SiGO / ADN / GAP-ETPE composite, its preparation method, and its application. The composite is prepared by solvent evaporation using amino-silicon functionalized graphene oxide, ammonium dinitramide, and poly(azide glycidyl ether) energetic thermoplastic elastomer. The average molecular weight of the poly(azide glycidyl ether) energetic thermoplastic elastomer is 20,000 to 30,000. The mass ratio of amino-silicon functionalized graphene oxide, ammonium dinitramide, and poly(azide glycidyl ether) energetic thermoplastic elastomer is 1:(3-7):(90-190). The NH-SiGO / ADN / GAP-ETPE composite prepared by this invention can improve the heat of explosion and heat of combustion of the original GAP-ETPE by 173.5 J / g to 589.0 J / g and the heat of combustion by 757.9 J / g to 1255.4 J / g. It can also reduce the impact sensitivity of GAP-ETPE from 9 J to 68 J to 100 J.

Description

Technical Field

[0001] This invention belongs to the field of energetic materials, specifically relating to an amino-functionalized graphene oxide (NH-SiGO) / ammonium dinitramide (ADN) / polyazoglycolic acid ether-based energetic thermoplastic elastomer (GAP-ETPE) composite, its preparation method, and its application. Background Technology

[0002] Energetic thermoplastic elastomers (ETPEs), used as binders for solid propellants, offer advantages such as high energy, insensitivity, low characteristic signal, and recyclability. Azide-based energetic thermoplastic elastomers have attracted widespread attention due to their high exothermic properties, oxygen-free decomposition, and good compatibility with nitramine explosives. Glycidyl ether azide (GAP)-based ETPEs are representative examples. Solid propellants based on GAP-ETPE binders have become a research hotspot for thermoplastic elastomer propellants. However, the high carbon content of GAP-ETPE chains leads to poor explosive and combustion performance, thus affecting the explosive and combustion performance of formulations using GAP-ETPE as a binder. Furthermore, the high azide group (-N3) content in GAP-ETPE results in high impact sensitivity, impacting its safety performance. In their patent "A Preparation Method of an Energetic Thermoplastic Elastomer Composite" (authorization number: ZL202010885160.4), Wang Yinglei et al. added amino-functionalized graphene oxide to GAP-ETPE, which improved the thermal stability of the original GAP-ETPE and reduced its glass transition temperature. However, the carbon content of the amino-functionalized graphene oxide was also high, and its addition could not improve the heat of explosion and heat of combustion of GAP-ETPE. Summary of the Invention

[0003] This invention provides an amino-functionalized graphene oxide (NH-SiGO) / ammonium dinitramide (ADN) / polyazoglycolic acid ether-based energetic thermoplastic elastomer (GAP-ETPE) composite, its preparation method, and its application. By introducing NH-SiGO and ADN into GAP-ETPE to prepare a composite, the explosion, combustion, and safety performance of GAP-ETPE can be improved by changing the amount of NH-SiGO and ADN added without changing the structure of GAP-ETPE.

[0004] To achieve the above-mentioned technical tasks, the present invention adopts the following technical solution:

[0005] An NH-SiGO / ADN / GAP-ETPE composite is prepared by solvent evaporation using amino-silicon functionalized graphene oxide, ammonium dinitramide, and poly(azide glycidyl ether)-based energetic thermoplastic elastomer. The average molecular weight of the poly(azide glycidyl ether)-based energetic thermoplastic elastomer is 20,000 to 30,000. The mass ratio of the amino-silicon functionalized graphene oxide, ammonium dinitramide, and poly(azide glycidyl ether)-based energetic thermoplastic elastomer is 1:(3 to 7):(90 to 190).

[0006] Optionally, the mass ratio of the aminosilicone functionalized graphene oxide, dinitramide ammonium, and polyazolidone glycidyl ether-based energetic thermoplastic elastomer is 1:5:100.

[0007] Optionally, the molecular structure of the GAP-ETPE is as follows:

[0008]

[0009] Where 30≤a, b, c≤45, and a, b, and c are all integers.

[0010] Optionally, the molecular structure of the NH-SiGO is shown below:

[0011]

[0012] Optionally, the molecular structure of the raw material ADN is shown below:

[0013]

[0014] The preparation method of the NH-SiGO / ADN / GAP-ETPE composite of the present invention includes the following steps:

[0015] Step 1: NH-SiGO is dispersed and dissolved in tetrahydrofuran to obtain NH-SiGO dispersion. The ratio of NH-SiGO to tetrahydrofuran is 10mg~60mg:20g~150g.

[0016] Step 2: Dissolve GAP-ETPE in tetrahydrofuran to obtain a clear GAP-ETPE solution. The ratio of GAP-ETPE to tetrahydrofuran is 4.0g-6.0g:100g-200g.

[0017] Step 3: Add ADN to N-methylpyrrolidone to obtain an ADN solution. The ratio of ADN to N-methylpyrrolidone is 0.06g~0.3g:10g~50g.

[0018] Step 4: After mixing the NH-SiGO dispersion and GAP-ETPE clear liquid, a mixed solution of NH-SiGO and GAP-ETPE is obtained;

[0019] Step 5: Add the ADN solution dropwise to the mixed solution of NH-SiGO and GAP-ETPE under stirring, mix well, and let stand and dry to obtain the composite.

[0020] Optionally, the solution preparation in steps 1-3 is carried out by stirring for 1-2 hours within a temperature range of 20-35°C.

[0021] Optionally, in step 4, the mixed solution is stirred at 20–40°C for 0.5–1 h.

[0022] Optionally, the dropping temperature in step 5 is 20-40°C. After the dropping is complete, the system is stirred for 0.5-1 hour, left to stand at room temperature for 1-2 weeks, and then dried at 30-40°C for 2-4 hours to obtain the composite.

[0023] The NH-SiGO / ADN / GAP-ETPE composite described in any one of the present invention is used in the preparation of solid propellant binders.

[0024] Compared with the prior art, the beneficial technical effects of this invention are as follows:

[0025] The NH-SiGO / ADN / GAP-ETPE composite prepared by the present invention can improve the heat of explosion and heat of combustion of the original GAP-ETPE by 173.5 J / g to 589.0 J / g and the heat of combustion by 757.9 J / g to 1255.4 J / g. It can also reduce the impact sensitivity of GAP-ETPE from 9 J to 68 J to 100 J.

[0026] The preparation method of the amino-functionalized graphene oxide (NH-SiGO) / ammonium dinitramide (ADN) / polyazoglycolic acid ether-based energetic thermoplastic elastomer (GAP-ETPE) composite of the present invention does not require changing the structure of GAP-ETPE, and can directly improve the explosion, combustion and safety performance of GAP-ETPE, with high reaction efficiency and low production cost. Attached Figure Description

[0027] The accompanying drawings are provided to further illustrate the present disclosure and form part of the specification. They are used together with the following detailed description to explain the present disclosure, but do not constitute a limitation thereof. In the drawings:

[0028] Figure 1 Here is a SEM image of the raw material GAP-ETPE composite prepared in Example 1 of this invention;

[0029] Figure 2 This is a SEM image of the NH-SiGO / ADN / GAP-ETPE composite prepared in Example 1 of the present invention.

[0030] Figure 3 Here is the IR spectrum of the raw material GAP-ETPE composite prepared in Example 1 of the present invention;

[0031] Figure 4 This is an IR spectrum of the NH-SiGO / ADN / GAP-ETPE composite prepared in Example 1 of the present invention. Detailed Implementation

[0032] The following detailed description of the present invention is exemplary and not intended to limit the scope of the invention. Based on the embodiments of the present invention, all non-inventory modifications made by those skilled in the art without departing from the present invention should be considered within the scope of protection of the present invention.

[0033] The amino-functionalized graphene oxide (NH-SiGO) / ammonium dinitramide (ADN) / polyazoglycolic acid ether-based energetic thermoplastic elastomer (GAP-ETPE) composite and its preparation method provided by this invention belong to the field of energetic materials technology.

[0034] The molecular structure of NH-SiGO is shown below:

[0035]

[0036] The molecular structure of the raw material ADN is shown below:

[0037]

[0038] The molecular structure of the raw material GAP-ETPE is shown below:

[0039]

[0040] Where 30≤a, b, c≤45, and a, b, and c are all integers.

[0041] ADN (chemical name: ammonium dinitramide) is a novel high-energy green oxidant composed of ammonium cations and dinitramide anions. It is a typical representative of third-generation energetic materials and has a high density (1.82 g / cm³). 3With advantages such as high oxygen coefficient (2.0), low sensitivity, and clean combustion fuel (halogen-free), ADN represents the international advanced level of high-energy oxidizers. Compared with common oxidizers such as ammonium perchlorate (AP), ADN has a higher enthalpy of formation (ADN: -1208 kJ / kg, AP: -2782 kJ / kg), and a smaller average relative molecular mass of combustion fuel (ADN: 26, AP: 31). The theoretical specific impulse of ADN-based solid propellants with the same mass content is 3s to 10s higher than that of AP-based solid propellants, representing the current international advanced level of high-energy propellants. It can be added to GAP-ETPE together with amino-functionalized graphene oxide to improve its explosion, combustion, and safety performance.

[0042] This invention uses NH-SiGO, ADN, and GAP-ETPE as raw materials and is prepared by solvent evaporation. The average molecular weight of the poly(azide glycidyl ether)-based energetic thermoplastic elastomer is 20,000–30,000. The mass ratio of amino-silicon functionalized graphene oxide, dinitramide ammonium, and poly(azide glycidyl ether)-based energetic thermoplastic elastomer is 1:(3–7):(90–190). The process includes the following steps: adding NH-SiGO to tetrahydrofuran and sonicating; adding GAP-ETPE... PE was added to tetrahydrofuran and stirred; ADN was added to N-methylpyrrolidone and stirred; NH-SiGO dispersion was poured into a mixed solution of GAP-ETPE and tetrahydrofuran and stirred; ADN solution was added dropwise to the mixed solution of NH-SiGO and GAP-ETPE, stirred evenly, and allowed to stand at room temperature for 1-2 weeks to obtain an amino-functionalized graphene oxide / ammonium dinitramide (ADN) / polyazoglycolic acid ether-based energetic thermoplastic elastomer (GAP-ETPE) composite. The NH-SiGO / ADN / GAP-ETPE composite prepared by this invention can improve the heat of explosion and heat of combustion of the original GAP-ETPE, increasing the heat of explosion by 173.5 J / g to 589.0 J / g and the heat of combustion by 757.9 J / g to 1255.4 J / g, and can also reduce the impact sensitivity of GAP-ETPE, decreasing it from 9 J to 68 J to 100 J.

[0043] The preparation method specifically includes the following steps:

[0044] Step 1: Prepare amino-silicon functionalized graphene oxide using the method described in the patent (application number 202010886213.4), wherein the main amino-silicon functionalized graphene oxide prepared is 3-aminopropyltriethoxysilane modified graphene oxide.

[0045] Step 2: Add NH-SiGO to tetrahydrofuran and ultrasonically disperse it for 1 to 2 hours in a temperature range of 20 to 35°C, wherein the ratio of NH-SiGO to tetrahydrofuran is 10 mg to 60 mg: 20 g to 150 g.

[0046] Step 3: Add GAP-ETPE to tetrahydrofuran and stir for 1 to 2 hours at a temperature range of 20 to 35°C. Filter out the insoluble matter to obtain GAP-ETPE clear liquid. The ratio of GAP-ETPE to tetrahydrofuran is 4.0 g to 6.0 g: 100 g to 200 g.

[0047] Step 4: Add ADN to N-methylpyrrolidone and stir at a temperature range of 20-35°C for 1-2 hours until ADN is completely dissolved to obtain an ADN-N-methylpyrrolidone solution; wherein the ratio of ADN to N-methylpyrrolidone is 0.06g-0.3g:10g-50g.

[0048] Step 5: Pour the NH-SiGO dispersion obtained in Step 2 into the mixed solution of GAP-ETPE and tetrahydrofuran obtained in Step 3, and stir the system at 20-40℃ for 0.5-1h. After the solution is homogeneous, the mixed solution of NH-SiGO and GAP-ETPE is obtained.

[0049] Step 6: The N-methylpyrrolidone solution of ADN obtained in Step 4 is added dropwise to the mixed solution of NH-SiGO and GAP-ETPE obtained in Step 5 under stirring. The dropwise addition temperature is 20-40℃. After the addition is complete, the system is stirred for 0.5-1h. After stirring evenly, the system is allowed to stand at room temperature for 1-2 weeks, and then dried at 30-40℃ for 2-4h to obtain the corresponding amino-functionalized graphene oxide (NH-SiGO) / ammonium dinitramide (ADN) / polyazoyl glycidyl ether-based energetic thermoplastic elastomer (GAP-ETPE) composite.

[0050] Graphene oxide, as a two-dimensional carbon nanostructure material, has attracted much attention in fields such as nanocomposites, sensors, hydrogen storage capacitors, and batteries. Amino-functionalized graphene oxide possesses extremely high mechanical properties, good biocompatibility, superior electron transport capabilities, and excellent electrochemical performance, making it a relatively ideal compound for improving the mechanical properties of materials.

[0051] In the raw materials involved in this invention, the graphene oxide raw material was purchased through the distributor Beijing Bailingwei Technology Co., Ltd. Ammonium dinitramide (ADN) was provided by Xi'an Modern Chemical Research Institute, with an impact sensitivity of 9 J. Glyceryl azidoether (GAP), with a relative molecular mass of 3000, was a commercially available product of Xi'an Modern Chemical Research Institute. The poly(glyceryl azidoether)-based energetic thermoplastic elastomer GAP-ETPE in the raw materials of this invention was prepared according to the method disclosed in the literature "Preparation and Properties of GAP-ETPE / NC Blend Polymers," Energetic Materials, 24(4):331-335. GAP-ETPE has a relative molecular mass of 20000-30000, a heat of explosion of 1826.6 J / g, a heat of combustion of 21758.9 J / g, and an impact sensitivity of 9 J.

[0052] Example 1:

[0053] Add 60 mg NH-SiGO to 150 g tetrahydrofuran and sonicate at 25 °C for 1.5 h. Add 6.0 g GAP-ETPE to 200 g tetrahydrofuran and stir at 25 °C for 1.5 h until GAP-ETPE is completely dissolved. Add 0.3 g ADN to 50 g N-methylpyrrolidone and stir at 25 °C for 1.5 h until ADN is completely dissolved. Pour the NH-SiGO dispersion into the GAP-ETPE mixed solution and stir the system at 30 °C for 1 h until the solution is homogeneous. Add the N-methylpyrrolidone solution of ADN dropwise to the mixed solution of GAP-ETPE and NH-SiGO while stirring at 30 °C. After adding the solution, stir for 1 h and then pour the mixture into a mold. After being left at room temperature for two weeks, the product was dried at 35°C for 3 hours to obtain 6.0 g of the corresponding amino-functionalized graphene oxide (NH-SiGO) / ammonium dinitramide (ADN) / polyazoyl glycidyl ether-based energetic thermoplastic elastomer (GAP-ETPE) composite. The heat of explosion of the NH-SiGO / ADN / GAP-ETPE composite was 2415.6 J / g, which was 589.0 J / g higher than that of GAP-ETPE; the heat of combustion was 23014.3 J / g, which was 1255.4 J / g higher than that of GAP-ETPE; and the impact sensitivity was 100 J, which was 91 J higher than that of GAP-ETPE.

[0054] Structural Analysis

[0055] (1) Scanning electron microscopy (SEM) analysis

[0056] Figure 1 This is a SEM image of the raw material GAP-ETPE prepared in Example 1. Figure 2This is a SEM image of the NH-SiGO / ADN / GAP-ETPE composite prepared in Example 1. The surface morphology of GAP-ETPE and its composite was studied using scanning electron microscopy. Pure GAP-ETPE is relatively smooth. When NH-SiGO and ADN are added, the GAP-ETPE composite becomes rougher, and ADN and NH-SiGO can be seen, while GAP-ETPE is coated on top.

[0057] (2) Infrared analysis

[0058] Figure 3 This is the IR spectrum of the raw material GAP-ETPE prepared in Example 1. Figure 4 This is the IR spectrum of the NH-SiGO / ADN / GAP-ETPE composite prepared in Example 1. As can be seen from the IR spectrum, the NH-SiGO / ADN / GAP-ETPE composite exhibits high IR density at 3057 cm⁻¹. -1 (NH4 + ), 1614cm -1 (NO2) and 1278cm -1 (NO2) showed characteristic peaks of ADN. With a small amount of NH-SiGO added, its characteristic peaks, such as the Si-O bond, were not obvious in the infrared, while other characteristic peaks, such as those of hydroxyl, carbonyl, and alkoxy functional groups, were also present in GAP-ETPE.

[0059] Example 2:

[0060] 11 mg of NH-SiGO was added to 20 g of tetrahydrofuran and ultrasonically dispersed at 20 °C for 1.5 h. 1.3 g of GAP-ETPE was added to 150 g of tetrahydrofuran and stirred at 25 °C for 1 h until GAP-ETPE was completely dissolved. 0.06 g of ADN was added to 25 g of N-methylpyrrolidone and stirred at 20 °C for 1 h until ADN was completely dissolved. The NH-SiGO dispersion was poured into the GAP-ETPE mixed solution, and the system was stirred at 25 °C for 0.5 h until the solution was homogeneous. The N-methylpyrrolidone solution of ADN was added dropwise to the GAP-ETPE and NH-SiGO mixed solution while stirring at 35 °C. After addition, the mixture was stirred for 0.5 h and then poured into a mold. After standing at room temperature for one week, the mixture was dried at 40 °C for 2 h to obtain 4.2 g of the corresponding NH-SiGO / ADN / GAP-ETPE complex. The heat of explosion of the NH-SiGO / ADN / GAP-ETPE composite is 2011.7 J / g, the heat of combustion is 22566.4 J / g, and the impact sensitivity is 69 J.

[0061] Example 3:

[0062] 19 mg of NH-SiGO was added to 20 g of tetrahydrofuran and ultrasonically dispersed at 22 °C for 1.5 h. 3.0 g of GAP-ETPE was added to 160 g of tetrahydrofuran and stirred at 25 °C for 1 h until the GAP-ETPE was completely dissolved. 0.09 g of ADN was added to 15 g of N-methylpyrrolidone and stirred at 20 °C for 1 h until the ADN was completely dissolved. The NH-SiGO dispersion was poured into the GAP-ETPE mixed solution, and the system was stirred at 25 °C for 0.5 h until the solution was homogeneous. The N-methylpyrrolidone solution of ADN was added dropwise to the GAP-ETPE and NH-SiGO mixed solution while stirring at 30 °C. After addition, the mixture was stirred for 0.5 h and then poured into a mold. After standing at room temperature for 2 weeks, the mixture was dried at 40 °C for 2 h to obtain 4.7 g of the corresponding NH-SiGO / ADN / GAP-ETPE complex. The heat of explosion of the NH-SiGO / ADN / GAP-ETPE composite is 2248.7 J / g, the heat of combustion is 23007.6 J / g, and the impact sensitivity is 74 J.

[0063] Example 4:

[0064] 28 mg of NH-SiGO was added to 40 g of tetrahydrofuran and ultrasonically dispersed at 25 °C for 1 h. 5.1 g of GAP-ETPE was added to 120 g of tetrahydrofuran and stirred at 24 °C for 1.5 h until the GAP-ETPE was completely dissolved. 0.15 g of ADN was added to 30 g of N-methylpyrrolidone and stirred at 25 °C for 1 h until the ADN was completely dissolved. The NH-SiGO dispersion was poured into the GAP-ETPE mixed solution, and the system was stirred at 30 °C for 1 h until the solution was homogeneous. The N-methylpyrrolidone solution of ADN was added dropwise to the GAP-ETPE and NH-SiGO mixed solution while stirring at 30 °C. After addition, the mixture was stirred for 1 h and then poured into a mold. After standing at room temperature for 2 weeks, the mixture was dried at 30 °C for 3 h to obtain 5.0 g of the corresponding NH-SiGO / ADN / GAP-ETPE complex. The heat of explosion of the NH-SiGO / ADN / GAP-ETPE composite is 2400.7 J / g, the heat of combustion is 22995.1 J / g, and the impact sensitivity is 77 J.

[0065] Example 5:

[0066] 33 mg of NH-SiGO was added to 80 g of tetrahydrofuran and ultrasonically dispersed at 25 °C for 1.5 h. 5.3 g of GAP-ETPE was added to 150 g of tetrahydrofuran and stirred at 20 °C for 1.5 h until the GAP-ETPE was completely dissolved. 0.19 g of ADN was added to 40 g of N-methylpyrrolidone and stirred at 25 °C for 1 h until the ADN was completely dissolved. The NH-SiGO dispersion was poured into the GAP-ETPE mixed solution, and the system was stirred at 35 °C for 0.5 h until the solution was homogeneous. The N-methylpyrrolidone solution of ADN was added dropwise to the GAP-ETPE and NH-SiGO mixed solution while stirring at 20 °C. After addition, the mixture was stirred for 1 h and then poured into a mold. After standing at room temperature for 2 weeks, the mixture was dried at 35 °C for 2 h to obtain 5.3 g of the corresponding NH-SiGO / ADN / GAP-ETPE complex. The heat of explosion of the NH-SiGO / ADN / GAP-ETPE composite is 2399.6 J / g, the heat of combustion is 22887.4 J / g, and the impact sensitivity is 87 J.

[0067] Example 6:

[0068] 41 mg of NH-SiGO was added to 110 g of tetrahydrofuran and ultrasonically dispersed at 25 °C for 2 h. 5.6 g of GAP-ETPE was added to 180 g of tetrahydrofuran and stirred at 20 °C for 1 h until the GAP-ETPE was completely dissolved. 0.22 g of ADN was added to 35 g of N-methylpyrrolidone and stirred at 25 °C for 1 h until the ADN was completely dissolved. The NH-SiGO dispersion was poured into the GAP-ETPE mixed solution, and the system was stirred at 25 °C for 1 h until the solution was homogeneous. The N-methylpyrrolidone solution of ADN was added dropwise to the GAP-ETPE and NH-SiGO mixed solution while stirring at 30 °C. After stirring for 1 h after the addition, the mixture was poured into a mold. After standing at room temperature for one week, it was dried at 30 °C for 4 h to obtain 5.5 g of the corresponding NH-SiGO / ADN / GAP-ETPE complex. The heat of explosion of the NH-SiGO / ADN / GAP-ETPE composite is 2407.4 J / g, the heat of combustion is 22994.7 J / g, and the impact sensitivity is 91 J.

[0069] Example 7:

[0070] 48 mg of NH-SiGO was added to 130 g of tetrahydrofuran and ultrasonically dispersed at 32 °C for 1 h. 5.7 g of GAP-ETPE was added to 160 g of tetrahydrofuran and stirred at 22 °C for 1.5 h until the GAP-ETPE was completely dissolved. 0.27 g of ADN was added to 40 g of N-methylpyrrolidone and stirred at 25 °C for 1 h until the ADN was completely dissolved. The NH-SiGO dispersion was poured into the GAP-ETPE mixed solution, and the system was stirred at 24 °C for 0.5 h until the solution was homogeneous. The N-methylpyrrolidone solution of ADN was added dropwise to the GAP-ETPE and NH-SiGO mixed solution while stirring at 35 °C. After addition, the mixture was stirred for 0.5 h and then poured into a mold. After standing at room temperature for one week, the mixture was dried at 30 °C for 3 h to obtain 5.6 g of the corresponding NH-SiGO / ADN / GAP-ETPE complex. The heat of explosion of the NH-SiGO / ADN / GAP-ETPE composite is 2388.1 J / g, the heat of combustion is 2288.1 J / g, and the impact sensitivity is 70 J.

[0071] Example 8:

[0072] 53 mg of NH-SiGO was added to 110 g of tetrahydrofuran and ultrasonically dispersed at 27 °C for 1 h. 4.8 g of GAP-ETPE was added to 170 g of tetrahydrofuran and stirred at 26 °C for 1 h until the GAP-ETPE was completely dissolved. 0.29 g of ADN was added to 35 g of N-methylpyrrolidone and stirred at 20 °C for 1 h until the ADN was completely dissolved. The NH-SiGO dispersion was poured into the GAP-ETPE mixed solution, and the system was stirred at 33 °C for 1 h until the solution was homogeneous. The N-methylpyrrolidone solution of ADN was added dropwise to the GAP-ETPE and NH-SiGO mixed solution while stirring at 36 °C. After addition, the mixture was stirred for 1 h and then poured into a mold. After standing at room temperature for 2 weeks, the mixture was dried at 34 °C for 2 h to obtain 4.7 g of the corresponding NH-SiGO / ADN / GAP-ETPE complex. The heat of explosion of the NH-SiGO / ADN / GAP-ETPE composite is 2077.5 J / g, the heat of combustion is 22886.7 J / g, and the impact sensitivity is 69 J.

[0073] Example 9:

[0074] 56 mg of NH-SiGO was added to 100 g of tetrahydrofuran and ultrasonically dispersed at 27 °C for 2 h. 5.9 g of GAP-ETPE was added to 160 g of tetrahydrofuran and stirred at 24 °C for 1 h until the GAP-ETPE was completely dissolved. 0.17 g of ADN was added to 40 g of N-methylpyrrolidone and stirred at 20 °C for 2 h until the ADN was completely dissolved. The NH-SiGO dispersion was poured into the GAP-ETPE mixed solution, and the system was stirred at 36 °C for 1 h until the solution was homogeneous. The N-methylpyrrolidone solution of ADN was added dropwise to the GAP-ETPE and NH-SiGO mixed solution while stirring at 30 °C. After stirring for 1 h after the addition, the mixture was poured into a mold. After standing at room temperature for 2 weeks, the mixture was dried at 30 °C for 3 h to obtain 4.8 g of the corresponding NH-SiGO / ADN / GAP-ETPE complex. The heat of explosion of the NH-SiGO / ADN / GAP-ETPE composite is 2347.2 J / g, the heat of combustion is 22991.7 J / g, and the impact sensitivity is 80 J.

[0075] Example 10:

[0076] 29 mg of NH-SiGO was added to 80 g of tetrahydrofuran and ultrasonically dispersed at 30 °C for 1.5 h. 4.3 g of GAP-ETPE was added to 120 g of tetrahydrofuran and stirred at 25 °C for 1 h until the GAP-ETPE was completely dissolved. 0.20 g of ADN was added to 30 g of N-methylpyrrolidone and stirred at 25 °C for 2 h until the ADN was completely dissolved. The NH-SiGO dispersion was poured into the GAP-ETPE mixed solution, and the system was stirred at 25 °C for 1 h until the solution was homogeneous. The N-methylpyrrolidone solution of ADN was added dropwise to the GAP-ETPE and NH-SiGO mixed solution while stirring at 25 °C. After stirring for 1 h after the addition, the mixture was poured into a mold. After being left at room temperature for 2 weeks, it was dried at 30 °C for 2 h to obtain 4.2 g of the corresponding NH-SiGO / ADN / GAP-ETPE complex. The heat of explosion of the NH-SiGO / ADN / GAP-ETPE composite is 2358.4 J / g, the heat of combustion is 22993.4 J / g, and the impact sensitivity is 91 J.

[0077] Although the present invention has been described in detail above with general descriptions and specific embodiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. An NH-SiGO / ADN / GAP-ETPE composite, characterized in that, The composite was prepared by solvent evaporation using aminosilicone-functionalized graphene oxide, ammonium dinitramide, and polyazoglycidyl ether-based energetic thermoplastic elastomer. The average molecular weight of polyazoglycidyl ether-based energetic thermoplastic elastomers is 20,000 to 30,000. The mass ratio of aminosilicone-functionalized graphene oxide, ammonium dinitramide, and polyazolidone-based energetic thermoplastic elastomer is 1:(3-7):(90-190).

2. The NH-SiGO / ADN / GAP-ETPE composite according to claim 1, characterized in that, The mass ratio of the aminosilicone functionalized graphene oxide, dinitramide ammonium, and polyazolidone glycidyl ether-based energetic thermoplastic elastomer is 1:5:

100.

3. The NH-SiGO / ADN / GAP-ETPE composite according to claim 1 or 2, characterized in that, The molecular structure of the GAP-ETPE is shown below: ； Where 30≤a, b, c≤45, and a, b, and c are all integers.

4. The NH-SiGO / ADN / GAP-ETPE composite according to claim 1 or 2, characterized in that, The molecular structure of the NH-SiGO is shown below: 。 5. The method for preparing the NH-SiGO / ADN / GAP-ETPE composite according to any one of claims 1-4, characterized in that, Includes the following steps: Step 1: NH-SiGO is dispersed and dissolved in tetrahydrofuran to obtain NH-SiGO dispersion. The ratio of NH-SiGO to tetrahydrofuran is 10 mg to 60 mg: 20 g to 150 g. Step 2: Dissolve GAP-ETPE in tetrahydrofuran to obtain a clear GAP-ETPE solution. The ratio of GAP-ETPE to tetrahydrofuran is 4.0g-6.0g:100g-200g. Step 3: Add ADN to N-methylpyrrolidone to obtain an ADN solution. The ratio of ADN to N-methylpyrrolidone is 0.06g~0.3g:10g~50g. Step 4: The NH-SiGO dispersion and the GAP-ETPE clear solution are mixed to obtain a mixed solution of NH-SiGO and GAP-ETPE; Step 5: Add the ADN solution dropwise to the mixed solution of NH-SiGO and GAP-ETPE under stirring, mix well, and let stand and dry to obtain the composite.

6. The method for preparing the NH-SiGO / ADN / GAP-ETPE composite according to claim 5, characterized in that, The solution preparation in steps 1-3 is carried out by stirring for 1-2 hours within a temperature range of 20-35℃.

7. The method for preparing the NH-SiGO / ADN / GAP-ETPE composite according to claim 5, characterized in that, In step 4, the mixed solution is stirred at 20–40°C for 0.5–1 h.

8. The method for preparing the NH-SiGO / ADN / GAP-ETPE composite according to claim 5, characterized in that, The dropping temperature in step 5 is 20-40℃. After the dropping is complete, the system is stirred for 0.5-1h, left to stand at room temperature for 1-2 weeks, and then dried at 30-40℃ for 2-4h to obtain the composite.

9. The application of the NH-SiGO / ADN / GAP-ETPE composite according to any one of claims 1-4 in the preparation of solid propellant binders.

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