3-aminopropyltriethoxysilane modified graphene oxide for reducing adn sensitivity

Abstract

The application discloses application of 3-aminopropyl triethoxysilane modified graphene oxide to reduction of sensitivity of ADN. The application uses 3-aminopropyl triethoxysilane modified graphene oxide to reduce the impact sensitivity of ADN and promote decomposition of ADN and improve thermal decomposition performance. Further, the prepared composite can not only reduce the impact sensitivity and friction sensitivity of ADN, but also promote decomposition of ADN and improve the mass loss of ADN.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of energetic materials, and particularly relates to the application of 3-aminopropyl triethoxysilane modified graphene oxide for reducing the sensitivity of ADN. BACKGROUND

[0002] ADN (chemical name: ammonium dinitramide) is a new type of high-energy green oxidizer composed of ammonium cation and dinitramide anion, which has the advantages of high density (1.82 g / cm 3 Compared with the common oxidizer ammonium perchlorate (AP), ADN has higher enthalpy of formation (ADN: -1208 kJ / kg, AP: -2782 kJ / kg), smaller average relative molecular mass of combustion gas (ADN: 26, AP: 31), and higher theoretical specific impulse of ADN-based solid propellant than that of AP-based solid propellant by 3s-10s. However, the application of ADN is limited due to its low sensitivity. SUMMARY

[0003] In view of the defects or deficiencies of the prior art, the present application provides the application of 3-aminopropyl triethoxysilane modified graphene oxide for reducing the friction sensitivity and impact sensitivity of ADN, accelerating the thermal decomposition of ADN or / and improving the mass loss of ADN.

[0004] The present application also provides a preparation method of 3-aminopropyl triethoxysilane modified graphene oxide / ADN composite, and the preparation method comprises the following steps:

[0005] Step 1, uniformly mix the gamma-butyrolactone solution of 3-aminopropyl triethoxysilane modified graphene oxide with the gamma-butyrolactone solution of ADN under the condition of 20-35℃ to obtain a mixed solution;

[0006] Step 2, drop the mixed solution obtained in step 1 into an organic solvent under the condition of 20-40℃; after the dropping is completed, collect the precipitate, and dry the precipitate at room temperature to obtain the 3-aminopropyl triethoxysilane modified graphene oxide / ADN composite; the organic solvent is selected from one or more than two kinds of mixture of dichloromethane, toluene, cyclohexane and trichloromethane.

[0007] Alternatively, the 3-aminopropyl triethoxysilane modified graphene oxide is added into gamma-butyrolactone, and a gamma-butyrolactone solution of graphene oxide is prepared by ultrasonic dispersion under the temperature condition of 20-35℃.

[0008] Alternatively, the ADN is added into gamma-butyrolactone, and a gamma-butyrolactone solution of ADN is prepared by stirring uniformly under the temperature condition of 20-35℃.

[0009] Alternatively, the 3-aminopropyl triethoxysilane modified graphene oxide gamma-butyrolactone solution is added into the ADN gamma-butyrolactone solution, and after stirring at 20-35 DEG C, ultrasonic dispersion is performed to obtain the mixture of step 1.

[0010] Alternatively, the use amount ratio of 3-aminopropyl triethoxysilane modified graphene oxide and gamma-butyrolactone in the 3-aminopropyl triethoxysilane modified graphene oxide gamma-butyrolactone solution is 4.0 mg-30 mg: 40 g-70 g; and the use amount ratio of ADN and gamma-butyrolactone in the ADN gamma-butyrolactone solution is 0.3 g-2.5 g: 10 g-40 g.

[0011] Alternatively, the use amount of the organic solvent is 500 g-1500 g.

[0012] The 3-aminopropyl triethoxysilane modified graphene oxide used in the application reduces the impact sensitivity of ADN, promotes the thermal decomposition of ADN, and improves the thermal decomposition performance.

[0013] Compared with ADN, the 3-aminopropyl triethoxysilane modified graphene oxide / ADN composite has a block structure, smooth edges and corners, and large and uniform particles; the impact sensitivity is reduced from 9.3 J to 16.8 J-28.5 J, the friction sensitivity is reduced from 72% to 18%-36%, the decomposition of ADN is promoted, the thermal decomposition temperature of ADN is advanced by 4.99 DEG C-13.46 DEG C, thereby the ADN can be rapidly decomposed to adjust the burning rate of the propellant formula; and the mass loss is increased by 10.94%-16.68%. BRIEF DESCRIPTION OF DRAWINGS

[0014] Figure 1 is the SEM image of ADN used in the embodiment of the application.

[0015] Figure 2 is the thermal decomposition DSC image (a) and TG image (b) of ADN used in the embodiment of the application.

[0016] Figure 3 is the SEM image of the NH-SiGO / ADN composite prepared in Example 1 of the application.

[0017] Figure 4 is the thermal decomposition DSC image (a) and TG image (b) of the NH-SiGO / ADN composite prepared in Example 1 of the application.

[0018] Figure 5 is the SEM image of the graphene / ADN composite prepared in Comparative Example 1 of the application.

[0019] Figure 6is a thermal decomposition DSC graph (a) and TG graph (b) of the graphene / ADN composite prepared in Inventive Example 1.

[0020] Figure 7 is a SEM graph of the reduced graphene oxide / ADN composite prepared in Inventive Example 2.

[0021] Figure 8 is a thermal decomposition DSC graph (a) and TG graph (b) of the reduced graphene oxide / ADN composite prepared in Inventive Example 2.

[0022] Figure 9 is a SEM graph of the carbon nanotube / ADN composite prepared in Inventive Example 3.

[0023] Figure 10 is a thermal decomposition DSC graph (a) and TG graph (b) of the carbon nanotube / ADN composite prepared in Inventive Example 3.

[0024] Figure 11 is a SEM graph of the composite prepared in Inventive Example 4.

[0025] Figure 12 is a SEM graph of the composite prepared in Inventive Example 5.

[0026] Figure 13 is a SEM graph of the composite prepared in Inventive Example 6.

[0027] Figure 14 is a SEM graph of the composite prepared in Inventive Example 7. DETAILED DESCRIPTION

[0028] Unless otherwise defined, scientific and technical terms used in this disclosure have the meanings that would be understood by one of ordinary skill in the art. It is to be understood that the present application may be implemented in various ways, including with respect to the selection of the specific reactants, the ratio of the reactants, the temperature and time of each step, the drying temperature and the calcination temperature, which are involved in the method of the present application, and which may be optimized by one skilled in the art based on the preparation of the carrier of the present application.

[0029] The 3-aminopropyltriethoxysilane modified graphene oxide (NH-SiGO) used in the following examples was prepared according to the method disclosed in CN202010886213.4; the graphene, reduced graphene oxide and carbon nanotube used in the following examples were purchased from the distributor Beijing Bailingwei Technology Co., Ltd.; ammonium dinitramide (ADN) was provided by Xi'an Institute of Modern Chemistry, with an impact sensitivity of 9.3 J, a friction sensitivity (66°, 2.5 MPa) of 72%, a thermal decomposition temperature of 195.07°C, and a mass loss of 83.17% in TG test. Among them Figure 1 and Figure 2The electron microscope image, thermal decomposition DSC graph (a) and thermal analysis TG graph (b) of ADN, respectively.

[0030] The impact sensitivity of the following examples was tested according to the impact sensitivity test method in GJB770A-97; the friction sensitivity was tested according to the friction sensitivity test method in GJB770A-97.

[0031] Example 1:

[0032] 4 mg of 3-aminopropyltrimethoxysilane modified graphene oxide (NH-SiGO) was added to 40 g of γ-butyrolactone and ultrasonically dispersed at 25°C for 1.5 h; 0.3 g of ADN was added to 10 g of γ-butyrolactone and stirred at 25°C for 15 min until the ADN was completely dissolved; the NH-SiGO dispersion was poured into the ADN solution, and the system was stirred at 30°C for 1 h and ultrasonically dispersed for 10 min.

[0033] The mixed solution of ADN and NH-SiGO was added dropwise to 500 g of dichloromethane under stirring at 30°C, the solution was filtered after the dropwise addition was completed, and was air-dried at room temperature until the weight was constant, to obtain 0.28 g of NH-SiGO / ADN composite.

[0034] It was detected that the impact sensitivity of the NH-SiGO / ADN composite prepared in the example was 19.7 J, the friction sensitivity was 25%, the thermal decomposition temperature was 185.71°C, and the thermal decomposition mass loss was 96.57%.

[0035] Example 2:

[0036] 13 mg of NH-SiGO was added to 60 g of γ-butyrolactone and ultrasonically dispersed at 21°C for 1.4 h; 0.7 g of ADN was added to 24 g of γ-butyrolactone and stirred at 27°C for 24 min until the ADN was completely dissolved; the NH-SiGO dispersion was poured into the ADN solution, and the system was stirred at 37°C for 0.6 h and ultrasonically dispersed for 17 min.

[0037] The mixed solution of ADN and NH-SiGO was added dropwise to 597 g of dichloromethane under stirring at 35°C, the solution was filtered after the dropwise addition was completed, and was air-dried at room temperature until the weight was constant, to obtain 0.58 g of NH-SiGO / ADN composite.

[0038] It was detected that the impact sensitivity of the NH-SiGO / ADN composite prepared in the example was 16.8 J, the friction sensitivity was 36%, the thermal decomposition temperature was 190.08°C, and the thermal decomposition mass loss was 94.11%.

[0039] Example 3:

[0040] NH-SiGO 27 mg was added into 70 g of γ-butyrolactone and dispersed by ultrasonic at 27 °C for 1.7 h; ADN 2.5 g was added into 40 g of γ-butyrolactone and stirred at 32 °C for 17 min until ADN was completely dissolved; the NH-SiGO dispersion was poured into the ADN solution, and the system was stirred at 27 °C for 0.7 h and dispersed by ultrasonic for 27 min;

[0041] The mixed solution of ADN and NH-SiGO was added dropwise into 1070 g of dichloromethane under stirring at 37 °C, and the solution was filtered after the dropwise addition was completed, and dried at room temperature to constant weight to obtain 2.4 g of NH-SiGO / ADN composite.

[0042] It was detected that the impact sensitivity of the NH-SiGO / ADN composite prepared in this example was 26.4 J, the friction sensitivity was 20%, the thermal decomposition temperature was 184.75 °C, and the thermal decomposition mass loss was 95.88%.

[0043] Example 4:

[0044] Step 1: 4.5 mg of 3-aminopropyltriethoxysilane modified graphene oxide (NH-SiGO) was added into 40 g of γ-butyrolactone and dispersed by ultrasonic at 25 °C for 1.5 h; ADN 0.3 g was added into 10 g of γ-butyrolactone and stirred at 25 °C for 15 min until ADN was completely dissolved; the NH-SiGO dispersion was poured into the ADN solution, and the system was stirred at 30 °C for 1 h and dispersed by ultrasonic for 10 min.

[0045] Step 2: The mixed solution of ADN and NH-SiGO obtained in step 1 was added dropwise into 500 g of dichloromethane under stirring at 30 °C, and the solution was filtered to collect the precipitate after the dropwise addition was completed, and dried at room temperature to constant weight to obtain 0.27 g of NH-SiGO / ADN composite.

[0046] It was detected that the impact sensitivity of the NH-SiGO / ADN composite prepared in this example was 28.5 J, the friction sensitivity was 18%, the thermal decomposition temperature was 181.61 °C, and the thermal decomposition mass loss was 99.85%, see Figure 3 .

[0047] Scanning electron microscope (SEM) analysis: Compared with Figure 1 the needle-like crystals of ADN solid shown in Figure 2 , the NH-SiGO / ADN composite showed a block structure and larger and more uniform particles, see

[0048] Comparative Example 1:

[0049] The difference between this comparative example and Example 4 is that NH-SiGO is replaced by graphene; the SEM analysis of the prepared composite is as followsFigure 5 as shown in FIG. 2.

[0050] The impact sensitivity of the compound prepared in the comparative example was 9.5 J, the friction sensitivity was 72%, the thermal decomposition temperature was 195.75°C, and the thermal decomposition mass loss was 93.76%, as shown in FIG. 3. Figure 6 as shown in FIG. 2.

[0051] Comparative Example 2:

[0052] The comparative example was different from Example 4 in that NH-SiGO was replaced by reduced graphene oxide; the SEM analysis of the prepared compound is shown in FIG. 2. Figure 7 as shown in FIG. 2.

[0053] The impact sensitivity of the compound prepared in the comparative example was 9.0 J, the friction sensitivity was 68%, the thermal decomposition temperature was 189.28°C, and the thermal decomposition mass loss was 92.52%, as shown in FIG. 3. Figure 8 as shown in FIG. 2.

[0054] Comparative Example 3:

[0055] The comparative example was different from Example 4 in that NH-SiGO was replaced by carbon nanotubes; the SEM analysis of the prepared compound is shown in FIG. 2. Figure 9 as shown in FIG. 2.

[0056] The impact sensitivity of the compound prepared in the comparative example was 8.0 J, the friction sensitivity was 64%, the thermal decomposition temperature was 194.55°C, and the thermal decomposition mass loss was 93.69%, as shown in FIG. 3. Figure 10 as shown in FIG. 2.

[0057] Comparative Example 4:

[0058] The comparative example was different from Example 4 in that γ-butyrolactone therein was replaced by tetrahydrofuran; the SEM analysis of the prepared compound is shown in FIG. 2. Figure 11 as shown in FIG. 2.

[0059] The impact sensitivity of the compound prepared in the comparative example was 8.2 J, the friction sensitivity was 69%, the thermal decomposition temperature was 195.24°C, and the thermal decomposition mass loss was 83.88%.

[0060] Comparative Example 5:

[0061] The comparative example was different from Example 4 in that γ-butyrolactone therein was replaced by N-methylpyrrolidone; the SEM analysis of the prepared compound is shown in FIG. 2. Figure 12 as shown in FIG. 2.

[0062] The impact sensitivity of the compound prepared in the comparative example was 7.4 J, the friction sensitivity was 66%, the thermal decomposition temperature was 194.66°C, and the thermal decomposition mass loss was 82.17%.

[0063] Comparative Example 6:

[0064] The difference between this comparative example and Example 4 is that in Step 1, 4.5 mg of NH-SiGO and ADN 0.3 g were added to 50 g of γ-butyrolactone, and stirred at 25°C for 1 hour 155 min; the SEM analysis of the prepared composite is shown in Figure 13 ;

[0065] The prepared composite was detected to have an impact sensitivity of 7.1 J, a friction sensitivity of 60%, a thermal decomposition temperature of 195.04°C, and a thermal decomposition mass loss of 81.19%.

[0066] Comparative Example 7:

[0067] The difference between this comparative example and Example 4 is that dichloromethane in Step 2 was replaced by 1,4-dioxane; the SEM analysis of the prepared composite is shown in Figure 14 ;

[0068] The prepared composite was detected to have an impact sensitivity of 9.5 J, a friction sensitivity of 73%, a thermal decomposition temperature of 194.87°C, and a thermal decomposition mass loss of 83.57%.

[0069] The detection results of the products prepared in the above examples and comparative examples are shown in Table 1.

[0070] Table 1

[0071]

[0072]

Claims

1. Use of 3-aminopropyltriethoxysilane modified graphene oxide for reducing friction sensitivity and impact sensitivity of ammonium dinitramide, accelerating thermal decomposition of ammonium dinitramide and improving mass loss of thermal decomposition of ammonium dinitramide.

2. A method for preparing a 3-aminopropyltriethoxysilane modified graphene oxide / diammonium nitroxyl complex, characterized by: The method comprises the following steps: Step 1, under the condition of 20-35℃, mix the γ-butyrolactone solution of 3-aminopropyltriethoxysilane modified graphene oxide and the γ-butyrolactone solution of ADN uniformly to obtain a mixed solution; Step 2, under the condition of 20-40℃, drop the mixed solution obtained in step 1 into an organic solvent; after the dropping is completed, collect the precipitate, dry at room temperature to obtain a 3-aminopropyltriethoxysilane modified graphene oxide / ammonium dinitramide composite; the organic solvent is selected from one or more than two kinds of mixture of dichloromethane, toluene, cyclohexane and trichloromethane.

3. The method for preparing 3-aminopropyltriethoxysilane-modified graphene oxide / diammonium nitroxyl complex according to claim 2, characterized by, The 3-aminopropyltriethoxysilane modified graphene oxide is added into γ-butyrolactone, and a γ-butyrolactone solution of graphene oxide is prepared by ultrasonic dispersion under the condition of 20-35℃.

4. The method of claim 2, wherein the preparation of 3-aminopropyltriethoxysilane modified graphene oxide / diammonium nitroxyl complex is characterized by, The ammonium dinitramide is added into γ-butyrolactone, and a γ-butyrolactone solution of ADN is prepared by stirring uniformly under the condition of 20-35℃.

5. The method of preparing 3-aminopropyltriethoxysilane modified graphene oxide / diammonium nitroxyl complex according to claim 2, characterized in that, The γ-butyrolactone solution of 3-aminopropyltriethoxysilane modified graphene oxide is added into the γ-butyrolactone solution of ADN, and the mixed solution obtained in step 1 is prepared by stirring under the condition of 20-35℃ and then ultrasonic dispersion.

6. The method of preparing 3-aminopropyltriethoxysilane modified graphene oxide / diammonium nitroxyl composite according to claim 2, characterized in that, The amount ratio of 3-aminopropyltriethoxysilane modified graphene oxide and γ-butyrolactone in the γ-butyrolactone solution of 3-aminopropyltriethoxysilane modified graphene oxide is 4.0mg-30mg:40g-70g; the amount ratio of ADN and γ-butyrolactone in the γ-butyrolactone solution of ADN is 0.3g-2.5g:10g-40g.

7. The method for preparing the 3-aminopropyltriethoxysilane-modified graphene oxide / dinitroamide ammonium composite according to claim 6, characterized in that, The amount of the organic solvent is 500g-1500g.

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