Guanidino formamide nitrate metal ion complex and preparation method thereof

Abstract

The invention relates to the technical field of energetic materials, and discloses a guanidino formamide nitrate metal ion complex and a preparation method thereof.The preparation method of the guanidino formamide nitrate metal ion complex comprises the following steps that dicyandiamide and water are mixed and heated, nitric acid is dropwise added, stirring is continued after dropwise adding is completed, and a mixture is obtained; reducing the temperature to room temperature to obtain a guanidinecarboxamide nitrate solution; adding carbonate of R into an acid guanidino formamide solution, heating, and continuously reacting; after the reaction is finished, filtering while hot; the guanidino formamide nitrate metal ion complex has the advantages that the burning rate and the gas production efficiency are higher, the sensitivity is low, and the stability is good; the preparation method of the guanidino formamide nitrate metal ion complex is simple in process, mild in condition, easy to prepare, safe and stable in raw material, small in danger and low in equipment requirement.

Description

Technical Field

[0001] The invention relates to the technical field of energetic materials, and in particular to a guanidinium nitrate formamide metal ion complex and a preparation method thereof. Background Art

[0002] Guanidine nitrate (GN) is an energetic material that is mostly white crystalline powder or granules. It is an important component of explosives and rocket propellants. The synthesis of guanidine nitrate is based on dicyandiamide and ammonium nitrate at 180℃-205℃. The product is obtained by crystallization and slicing. The reaction temperature is high and the reaction raw materials are dangerous. Through research, it is found that guanidine nitrate solid propellant has the disadvantage of low burning rate. Ivan V. Mendenhall (US, 20050098246) and others found that transition metal oxides such as manganese oxide and iron oxide can improve the performance of energetic materials; Han Zhiyue (Journal of Ordnance Equipment Engineering, 2018, 39 (5): 172-178.) found that introducing oxygen atoms into azole, guanidine and azine molecules can improve performance, but there is still the problem of poor stability. Summary of the invention

[0003] The purpose of the present invention is to solve the shortcomings of the prior art and to propose a guanidinium nitrate formamide metal ion complex and a preparation method thereof.

[0004] In order to achieve the above object, the present invention adopts the following technical solutions: A guanidinium nitrate carboxamide metal ion complex, wherein the guanidinium nitrate carboxamide metal ion complex has the following structure:

[0005] In the structure, R is a divalent cation of a transition metal.

[0006] Preferably, the R comprises Mn 2+ , Fe 2+ 、Co 2+ , Cu 2+ 、Zn 2+ One of them.

[0007] The above-mentioned method for preparing a guanidinium nitrate formamide metal ion complex comprises the following steps: Step 1: Mix dicyandiamide: water in a ratio of (35%-45%): (65%-55%) by mass, heat, drop nitric acid, continue stirring for 1h-1.5h after the addition, and cool the temperature to room temperature to obtain guanidine formamide nitrate solution; Step 2: Add the carbonate of R into the acid guanidine formamide solution at 30°C-40°C for 1h-3h, heat to 50°C-100°C, and continue the reaction for 2h-12h; Step 3: After the reaction is completed, filter while hot; Step 4: The filtered product is vacuum dried to obtain a guanidinium nitrate formamide metal ion complex.

[0008] Preferably, the carbonate of R in step 2 is industrial grade with a purity of 99%.

[0009] Preferably, the nitric acid in step 1 is fuming nitric acid, and the amount of fuming nitric acid added is 2.05-2.2 of the molar mass of the carbonate of R.

[0010] Preferably, the heating temperature in step 1 is 50°C-100°C.

[0011] Preferably, in step 2, the molar ratio of guanidinium carboxamide nitrate to the carbonate of R is 2:(1-1.3).

[0012] Preferably, in step 3, the filtration temperature is 50°C-70°C.

[0013] Preferably, in step 4, the drying temperature is 50°C-70°C.

[0014] Preferably, in the preparation method of the above-mentioned guanidinium nitrate formamide metal ion complex, the chemical reaction formula is as follows: .

[0015] Preferably, in the method for preparing the guanidinium nitrate carboxamide metal ion complex of the present invention, the amount of fuming nitric acid added is limited to 2.0-2.2 of the molar mass of the carbonate of R, because it is ensured that dicyandiamide can be hydrolyzed as much as possible in an acidic environment to generate guanidinium nitrate carboxamide, and at the same time, it is ensured that the carbonate of R can react as completely as possible, thereby ensuring that more metal cations can undergo complexation reaction.

[0016] The beneficial effects of the present invention are: 1. The guanidinium nitrate formamide metal ion complex of the present invention has higher combustion rate and gas production efficiency.

[0017] 2. The guanidinium nitrate formamide metal ion complex of the present invention has low sensitivity and good stability.

[0018] 3. The method for preparing the guanidinium nitrate formamide metal ion complex of the present invention has simple process, mild conditions and easy preparation, safe and stable raw materials, low risk and low equipment requirements. DETAILED DESCRIPTION

[0019] The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Embodiment 1:

[0020] The guanidinium nitrate formamide ferrous ion complex described in this embodiment has the structure shown below:

[0021] The preparation method of the guanidinium nitrate formamide ferrous ion complex described in this embodiment comprises the following steps: Heat 0.5kg of dicyandiamide and 4.5kg of water to 70℃, add 0.43kg of fuming nitric acid dropwise after complete dissolution, and continue stirring for 1h after the addition is complete. When the temperature drops to 30℃, add 0.38kg of ferrous carbonate, and add it within 1h. Raise the system temperature to 85℃, react for 5h, stop heating, wait for the system to cool to 50℃, filter while hot, and vacuum dry at 60℃ to obtain 1.04kg of guanidinium nitrate ferrous ion complex, with a yield (based on guanidinium nitrate) of 91.0%. Embodiment 2:

[0022] The guanidinium nitrate formamide ferrous ion complex described in this embodiment has the structure shown below:

[0023] The preparation method of the guanidinium nitrate carboxamide manganese ion complex described in this embodiment comprises the following steps: Heat 0.8 kg of dicyandiamide and 7.2 kg of water to 60°C. After complete dissolution, add 0.67 kg of fuming nitric acid dropwise. Continue stirring for 1.2 hours after the addition is complete. When the temperature drops to 35°C, add 0.59 kg of manganese carbonate. Add the mixture within 1.5 hours. Raise the system temperature to 75°C, react for 3.5 hours, stop heating, wait for the system to cool to 50°C, filter while hot, and dry under vacuum at 55°C to obtain 1.69 kg of guanidinium nitrate carboxamide manganese ion complex. The yield (based on guanidinium nitrate carboxamide) is 92.7%. Embodiment 3:

[0024] The guanidinium nitrate formamide ferrous ion complex described in this embodiment has the structure shown below:

[0025] The preparation method of the guanidinium nitrate formamide cobalt ion complex described in this embodiment comprises the following steps: Heat 0.4kg of dicyandiamide and 2.1kg of water to 65℃, add 0.35kg of fuming nitric acid dropwise after complete dissolution, and continue stirring for 1.2h after the addition is complete. When the temperature drops to 32℃, add 0.32kg of cobalt carbonate, and add it within 1.5h. Raise the system temperature to 85℃, react for 6h, stop heating, wait for the system to cool to 60℃, filter while hot, and vacuum dry at 65℃ to obtain 0.83kg of guanidinium nitrate ferrocobalt complex, with a yield (based on guanidinium nitrate) of 90.5%. Embodiment 4:

[0026] The guanidinium nitrate formamide ferrous ion complex described in this embodiment has the structure shown below:

[0027] The preparation method of the guanidinium nitrate formamide copper ion complex described in this embodiment comprises the following steps: Heat 1kg of dicyandiamide and 4kg of water to 80℃, add 0.94kg of fuming nitric acid dropwise after complete dissolution, and continue stirring for 1.5h after the addition is complete. When the temperature drops to 40℃, add 0.88kg of copper carbonate, and add it within 2h. Raise the system temperature to 95℃, react for 7h, stop heating, wait for the system to cool to 65℃, filter while hot, and vacuum dry at 70℃ to obtain 2.09kg of guanidinium nitrate copper ion complex, with a yield (based on guanidinium nitrate) of 89.6%. Embodiment 5:

[0028] The guanidinium nitrate formamide ferrous ion complex described in this embodiment has the structure shown below:

[0029] The preparation method of the guanidinium nitrate carboxamide zinc ion complex described in this embodiment comprises the following steps: Heat 1.2 kg of dicyandiamide and 6.3 kg of water to 75°C. After complete dissolution, add 1.28 kg of fuming nitric acid dropwise. Continue stirring for 1 hour after the addition is complete. When the temperature drops to 30°C, add 1.16 kg of zinc carbonate. Add the entire amount within 2 hours. Raise the system temperature to 98°C, react for 8 hours, stop heating, wait for the system to cool to 65°C, filter while hot, and dry under vacuum at 70°C to obtain 2.43 kg of guanidinium nitrate formamide zinc ion complex. The yield (based on guanidinium nitrate formamide) is 86.6%.

[0030] The main infrared absorption peaks of the guanidinium nitrate formamide metal ion complex of the present invention are shown in Table 1:

[0031] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A guanidinium nitrate formamide metal ion complex, characterized in that: The guanidine nitrate formamide metal ion complex has the following structure: ； In the structure, R is a divalent cation of a transition metal.

2. A guanidinium nitrate formamide metal ion complex according to claim 1, characterized in that: The R includes Mn 2+ , Fe 2+ 、Co 2+ , Cu 2+ 、Zn 2+ One of them.

3. A method for preparing a guanidinium nitrate formamide metal ion complex as described in any one of claims 1-2, characterized in that: The following steps are involved: Step 1: Mix dicyandiamide: water in a ratio of (35%-45%): (65%-55%) by mass, heat, drop nitric acid, continue stirring for 1h-1.5h after the addition, and cool the temperature to room temperature to obtain guanidine formamide nitrate solution; Step 2: Add the carbonate of R into the acid guanidine formamide solution at 30°C-40°C for 1h-3h, heat to 50°C-100°C, and continue the reaction for 2h-12h; Step 3: After the reaction is completed, filter while hot; Step 4: The filtered product is vacuum dried to obtain a guanidinium nitrate formamide metal ion complex.

4. The method for preparing a guanidinium nitrate formamide metal ion complex according to claim 3, characterized in that: The carbonate of R in step 2 is industrial grade with a purity of 99%.

5. The method for preparing a guanidinium nitrate formamide metal ion complex according to claim 3, characterized in that: The nitric acid in step 1 is fuming nitric acid, and the amount of fuming nitric acid added is 2.05-2.2 of the molar mass of the carbonate of R.

6. The method for preparing a guanidinium nitrate formamide metal ion complex according to claim 3, characterized in that: The heating temperature of step 1 is 50°C-100°C.

7. The method for preparing a guanidinium nitrate formamide metal ion complex according to claim 3, characterized in that: In step 2, the molar ratio of guanidinium carboxamide nitrate to the carbonate of R is 2:(1-1.3).

8. The method for preparing a guanidinium nitrate formamide metal ion complex according to claim 3, characterized in that: In step 3, the filtration temperature is 50°C-70°C.

9. The method for preparing a guanidinium nitrate formamide metal ion complex according to claim 3, characterized in that: In step 4, the drying temperature is 50°C-70°C.

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