Application of 3-aminopropyltriethoxysilane modified graphene oxide to reduction of ADN sensitivity

Abstract

The invention discloses an application of 3-aminopropyltriethoxysilane modified graphene oxide in reduction of ADN (adenosine diphosphate) sensitivity and an application of the 3-aminopropyltriethoxysilane modified graphene oxide in reduction of ADN sensitivity. According to the invention, the 3-aminopropyltriethoxysilane modified graphene oxide is used, so that the impact sensitivity of ammonium dinitramide is reduced, the decomposition of ADN is promoted, and the thermal decomposition performance is improved. The further prepared compound not only can reduce the impact sensitivity and friction sensitivity of the ADN, but also can promote decomposition of the ADN and improve the mass loss of the ADN.

Description

Technical Field

[0001] The invention belongs to the field of energetic materials, and in particular relates to the application of 3-aminopropyltriethoxysilane-modified graphene oxide for reducing ADN sensitivity. Background Art

[0002] ADN (chemical name: ammonium dinitramide) is a new type of high-energy green oxidant composed of ammonium cations and dinitramide anions. It has a high density (1.82g / cm 3 ), high oxygen coefficient (2.0), clean fuel gas (halogen-free), etc. Compared with the common oxidant ammonium perchlorate (AP), ADN has a higher formation enthalpy (ADN: -1208kJ / kg, AP: -2782kJ / kg), a smaller average relative molecular mass of fuel gas (ADN: 26, AP: 31), and the theoretical specific impulse of ADN-based solid propellant with the same mass content is 3s to 10s higher than that of AP-based solid propellant. However, its application is limited due to its low sensitivity. Summary of the invention

[0003] In view of the defects or shortcomings of the prior art, the present invention provides an application of 3-aminopropyltriethoxysilane modified graphene oxide for reducing the friction sensitivity and impact sensitivity of ammonium dinitramide, accelerating the thermal decomposition of ammonium dinitramide and / or increasing the mass loss of ammonium dinitramide.

[0004] The present invention also provides a method for preparing a 3-aminopropyltriethoxysilane-modified graphene oxide / ammonium dinitramide composite, and the provided preparation method comprises the following steps:

[0005] Step 1, at 20-35° C., uniformly mix a γ-butyrolactone solution of 3-aminopropyltriethoxysilane-modified graphene oxide and a γ-butyrolactone solution of ADN to obtain a mixed solution;

[0006] Step 2, under the condition of 20-40° C., the mixed solution obtained in step 1 is added dropwise to an organic solvent; after the addition is completed, the precipitate is collected and dried at room temperature to obtain a 3-aminopropyltriethoxysilane-modified graphene oxide / ammonium dinitramide complex; the organic solvent is selected from one or a mixture of two or more of dichloromethane, toluene, cyclohexane and chloroform.

[0007] An optional scheme is to add 3-aminopropyltriethoxysilane-modified graphene oxide to γ-butyrolactone and perform ultrasonic dispersion at a temperature of 20 to 35° C. to obtain a γ-butyrolactone solution of graphene oxide.

[0008] An optional solution is to add ammonium dinitramide to γ-butyrolactone and stir the mixture evenly at a temperature of 20 to 35° C. to obtain a γ-butyrolactone solution of ADN.

[0009] An optional solution is to add the γ-butyrolactone solution of 3-aminopropyltriethoxysilane-modified graphene oxide to the γ-butyrolactone solution of ADN, stir at 20-35° C. and then perform ultrasonic dispersion to obtain the mixed solution obtained in step 1.

[0010] An optional scheme is that the usage 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 usage ratio of ADN and γ-butyrolactone in the γ-butyrolactone solution of ADN is 0.3g~2.5g:10g~40g.

[0011] An optional solution is that the amount of organic solvent used is 500g to 1500g.

[0012] The present invention adopts 3-aminopropyltriethoxysilane to modify graphene oxide, thereby reducing the ADN impact sensitivity, promoting the thermal decomposition of ADN, and improving the thermal decomposition performance.

[0013] Compared with ADN, the 3-aminopropyltriethoxysilane modified graphene oxide / ADN composite of the invention has a block structure, smoother edges and corners, larger particles and more uniformity; the impact sensitivity is reduced from 9.3 J to 16.8 J to 28.5 J, the friction sensitivity is reduced from 72% to 18% to 36%, and the decomposition of ADN can be promoted. The thermal decomposition temperature of ADN is advanced by 4.99° C. to 13.46° C., thereby promoting the rapid decomposition of ADN, thereby adjusting the burning rate of the propellant formula; and the mass loss is increased by 10.94% to 16.68%. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 is a SEM image of ADN used in the embodiments of the present invention.

[0015] Figure 2 The thermal decomposition DSC graph (a) and TG graph (b) of ADN used in the examples of the present invention are shown.

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

[0017] Figure 4 The thermal decomposition DSC graph (a) and TG graph (b) of the NH-SiGO / ADN composite prepared in Example 1 of the present invention are shown.

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

[0019] Figure 6The thermal decomposition DSC graph (a) and TG graph (b) of the graphene / ADN composite prepared in Comparative Example 1 of the present invention are shown.

[0020] Figure 7 It is a SEM image of the reduced graphene oxide / ADN composite prepared in Comparative Example 2 of the present invention.

[0021] Figure 8 The thermal decomposition DSC graph (a) and TG graph (b) of the reduced graphene oxide / ADN composite prepared in Comparative Example 2 of the present invention are shown.

[0022] Fig. 9 It is a SEM picture of the carbon nanotube / ADN composite prepared in Comparative Example 3 of the present invention.

[0023] Fig.10 The thermal decomposition DSC graph (a) and TG graph (b) of the carbon nanotube / ADN composite prepared in Comparative Example 3 of the present invention are shown.

[0024] Fig.11 is a SEM image of the composite prepared in Comparative Example 4 of the present invention.

[0025] Fig.12 is a SEM image of the composite prepared in Comparative Example 5 of the present invention.

[0026] Fig.13 is a SEM image of the composite prepared in Comparative Example 6 of the present invention.

[0027] Fig.14 is a SEM image of the composite prepared in Comparative Example 7 of the present invention. DETAILED DESCRIPTION

[0028] Unless otherwise specified, the scientific and technical terms in this article are understood according to the knowledge of ordinary technicians in the relevant fields. It should be noted that based on the carrier preparation scheme of the present invention, those skilled in the art can optimize the methods of the present invention, including but not limited to specific reactants, ratios of reactants in each step, temperature and duration, drying temperature and calcination temperature to achieve the relevant effects of the carrier of the present invention.

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

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

[0031] Embodiment 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 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. After the addition was completed, the solution was filtered and dried at room temperature to constant weight to obtain 0.28 g of NH-SiGO / ADN composite.

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

[0035] Embodiment 2:

[0036] 13 mg NH-SiGO was added to 60 g γ-butyrolactone and ultrasonically dispersed at 21 °C for 1.4 h. 0.7 g ADN was added to 24 g γ-butyrolactone and stirred at 27 °C for 24 min until 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. After the addition was complete, the solution was filtered and dried at room temperature to constant weight to obtain 0.58 g of NH-SiGO / ADN composite.

[0038] According to the test, the impact sensitivity of the NH-SiGO / ADN composite prepared in this embodiment is 16.8 J, the friction sensitivity is 36%, the thermal decomposition temperature is 190.08° C., and the thermal decomposition mass loss is 94.11%.

[0039] Embodiment 3:

[0040] 27 mg NH-SiGO was added to 70 g γ-butyrolactone and ultrasonically dispersed at 27 °C for 1.7 h. 2.5 g ADN was added to 40 g 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 ultrasonically dispersed for 27 min.

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

[0042] According to the test, the impact sensitivity of the NH-SiGO / ADN composite prepared in this embodiment is 26.4 J, the friction sensitivity is 20%, the thermal decomposition temperature is 184.75° C., and the thermal decomposition mass loss is 95.88%.

[0043] Embodiment 4:

[0044] Step 1, add 4.5 mg 3-aminopropyltriethoxysilane modified graphene oxide (NH-SiGO) to 40 g γ-butyrolactone, and ultrasonically disperse at 25°C for 1.5 h; add 0.3 g ADN to 10 g γ-butyrolactone, stir at 25°C for 15 min, and wait until ADN is completely dissolved; pour the NH-SiGO dispersion into the ADN solution, stir the system at 30°C for 1 h, and ultrasonically disperse for 10 min;

[0045] Step 2: Add the mixed solution of ADN and NH-SiGO obtained in step 1 dropwise into 500 g of dichloromethane under stirring at 30° C. After the addition is complete, filter the solution to collect the precipitate, and dry it at room temperature to constant weight to obtain 0.27 g of NH-SiGO / ADN composite.

[0046] After testing, the impact sensitivity of the NH-SiGO / ADN composite prepared in this embodiment is 28.5J, the friction sensitivity is 18%, the thermal decomposition temperature is 181.61°C, and the thermal decomposition mass loss is 99.85%. Figure 3 shown.

[0047] Scanning electron microscopy (SEM) analysis: compared with Figure 1 The ADN solid shown is a needle-shaped crystal with uneven particles. The NH-SiGO / ADN composite has a block structure with larger and more uniform particles. Figure 2 shown.

[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 follows Figure 5 As shown;

[0050] After testing, the impact sensitivity of the composite prepared in this comparative example is 9.5 J, the friction sensitivity is 72%, the thermal decomposition temperature is 195.75°C, and the thermal decomposition mass loss is 93.76%. Figure 6 shown.

[0051] Comparative Example 2:

[0052] The difference between this comparative example and Example 4 is that NH-SiGO is replaced by reduced graphene oxide; the SEM analysis of the prepared composite is as follows: Figure 7 As shown;

[0053] After testing, the composite prepared in this comparative example has an impact sensitivity of 9.0 J, a friction sensitivity of 68%, a thermal decomposition temperature of 189.28°C, and a thermal decomposition mass loss of 92.52%. Figure 8 shown.

[0054] Comparative Example 3:

[0055] The difference between this comparative example and Example 4 is that NH-SiGO is replaced by carbon nanotubes; the SEM analysis of the prepared composite is as follows: Fig. 9 As shown;

[0056] After testing, the composite prepared in this comparative example has an impact sensitivity of 8.0 J, a friction sensitivity of 64%, a thermal decomposition temperature of 194.55°C, and a thermal decomposition mass loss of 93.69%. Fig.10 shown.

[0057] Comparative Example 4:

[0058] The difference between this comparative example and Example 4 is that the γ-butyrolactone is replaced by tetrahydrofuran; the SEM analysis of the prepared composite is as follows: Fig.11 As shown;

[0059] The results show that the impact sensitivity of the prepared composite is 8.2 J, the friction sensitivity is 69%, the thermal decomposition temperature is 195.24°C, and the thermal decomposition mass loss is 83.88%.

[0060] Comparative Example 5:

[0061] The difference between this comparative example and Example 4 is that γ-butyrolactone is replaced by N-methylpyrrolidone; the SEM analysis of the prepared composite is as follows: Fig.12 As shown;

[0062] The results show that the impact sensitivity of the prepared composite is 7.4 J, the friction sensitivity is 66%, the thermal decomposition temperature is 194.66°C, and the thermal decomposition mass loss is 82.17%.

[0063] Comparative Example 6:

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

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

[0066] Comparative Example 7:

[0067] The difference between this comparative example and Example 4 is that the dichloromethane in step 2 is replaced with 1,4-dioxane; the SEM analysis of the prepared composite is as follows: Fig.14 As shown;

[0068] The results show that the impact sensitivity of the prepared composite is 9.5 J, the friction sensitivity is 73%, the thermal decomposition temperature is 194.87°C, and the thermal decomposition mass loss is 83.57%.

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

[0070] Table 1

[0071]

[0072]

Claims

1. 3-Aminopropyltriethoxysilane modified graphene oxide is used to reduce the friction sensitivity and impact sensitivity of ammonium dinitramide, accelerate the thermal decomposition of ammonium dinitramide and / or increase the mass loss of ammonium dinitramide.

2. A method for preparing a 3-aminopropyltriethoxysilane modified graphene oxide / ammonium dinitramide composite, characterized in that: The method comprises the following steps: Step 1, at 20-35° C., uniformly mix a γ-butyrolactone solution of 3-aminopropyltriethoxysilane-modified graphene oxide and a γ-butyrolactone solution of ADN to obtain a mixed solution; Step 2, under the condition of 20-40° C., the mixed solution obtained in step 1 is added dropwise to an organic solvent; after the addition is completed, the precipitate is collected and dried at room temperature to obtain a 3-aminopropyltriethoxysilane-modified graphene oxide / ammonium dinitramide complex; the organic solvent is selected from one or a mixture of two or more of dichloromethane, toluene, cyclohexane and chloroform.

3. The method for preparing the 3-aminopropyltriethoxysilane modified graphene oxide / ammonium dinitramide composite according to claim 2, characterized in that: 3-aminopropyltriethoxysilane-modified graphene oxide is added into gamma-butyrolactone, and ultrasonic dispersion is performed at a temperature of 20 to 35° C. to prepare a gamma-butyrolactone solution of graphene oxide.

4. The method for preparing the 3-aminopropyltriethoxysilane modified graphene oxide / ammonium dinitramide composite according to claim 2, characterized in that: Add ammonium dinitramide to γ-butyrolactone, and stir evenly at a temperature of 20-35° C. to prepare a γ-butyrolactone solution of ADN.

5. The method for preparing the 3-aminopropyltriethoxysilane modified graphene oxide / ammonium dinitramide composite according to claim 2, characterized in that: The γ-butyrolactone solution of 3-aminopropyltriethoxysilane-modified graphene oxide is added to the γ-butyrolactone solution of ADN, and the mixture is dispersed by ultrasonication after stirring at 20-35° C. to obtain the mixed solution obtained in step 1.

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

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