One-step synthesis method of 4, 4 ', 6, 6'-tetra (hydrazino) hydrazine-1, 3, 5-triazine

Abstract

The invention discloses a one-step synthesis method of 4, 4 ', 6, 6'-tetra (hydrazino) hydrazine-1, 3, 5-triazine, which comprises the following steps: pre-cooling a hydrazine hydrate ethylene glycol solution, adding cyanuric chloride ethylene glycol suspension, reacting, filtering, washing and drying to obtain the 4, 4 ', 6, 6'-tetra (hydrazino) hydrazine-1, 3, 5-triazine. The intermediate 4, 4 ', 6, 6'-tetrakis (hydrazino) hydrazine-1, 3, 5-triazine of the triazine high-nitrogen energetic material is simply and efficiently synthesized through a one-step method with cyanuric chloride as a raw material and ethylene glycol as a dispersing agent and a buffering agent, organic solvents such as tetrahydrofuran and acetonitrile are not involved in the synthesis process any more, the reaction is mild, the process is green and environmentally friendly, and follow-up treatment is simple. By adding the ethylene glycol, the feeding mode of directly feeding the solid powder in the prior art is changed, rapid and continuous fed-batch feeding is realized, and industrial production is easier to realize.

Description

Technical Field

[0001] The invention belongs to the technical field of energetic materials, and particularly relates to a one-step synthesis method of a triazine high-nitrogen compound. Technical Background

[0002] High nitrogen energetic compounds have gradually become an important direction in the field of energetic materials research due to their superior performance. In the synthesis route of high nitrogen energetic compounds, the synthesis of intermediates is an important factor that determines the purity, production cost, feasibility, etc. of the compound. 4,4',6,6'-Tetra(hydrazino)hydrazine-1,3,5-triazine was first synthesized and reported by Huynh M.H. et al. of Los Alamos National Laboratory in the United States in 2004, and further synthesized high nitrogen energetic materials 4,4',6,6'-tetra(azido)hydrazine-1,3,5-triazine and 4,4',6,6'-tetra(azido)azo-1,3,5-triazine (Scheme 1) (see Figure 1 )[Reference 1]. Subsequently, domestic scholars Li Xiaotong and others also conducted relevant research on this intermediate and subsequent high nitrogen energy-containing materials and their synthetic routes[References 2, 3].

[0003] In summary, in order to synthesize the subsequent 4,4',6,6'-tetrakis (azido) hydrazine-1,3,5-triazine and 4,4',6,6'-tetrakis (azido) azo-1,3,5-triazine, the intermediate 4,4',6,6'-tetrakis (hydrazine) hydrazine-1,3,5-triazine is the key in the synthesis route. The synthesis method of this compound reported in the literature is divided into two steps, and acetonitrile and tetrahydrofuran are used as reaction solvents in large quantities, respectively. The reaction is violent and there are huge safety risks. If industrialized production is scaled up, the two-step synthesis is difficult to control, and the recovery and treatment of a large amount of waste solvents will incur high costs and cause certain harm to the environment, which limits the synthesis of the intermediate 4,4',6,6'-tetrakis (hydrazine) hydrazine-1,3,5-triazine and becomes an obstacle to industrial application.

[0004] References:

[0005] [1]Huynh MH,Hiskey MA,Hartline EL,Montoya DP,GilardiR.Polyazido high-nitrogencompounds:hydrazo and azo-1,3,5-triazine.Angew.Chem.2004,116:5032-5036.

[0006] [2] Li Xiaotong, Pang Siping, Yu Yongzhong, Luo Yunjun, High nitrogen compound 4,4′,6,6′-tetraazidoazo-1,3,5-triazine

[0007] Synthesis Research, Energetic Materials, 2007, 15(5): 485-489.

[0008] [3]Li XT, Li SH, Pang SP, Yu YZ, Luo YJA new dfficient route for the synthesis of 4,4'6,6'-tetra-(azido)azo-1,3,5-triazine, Chinese Chemical Letter, 2007,18:1037-1039. Summary of the invention

[0009] In order to overcome the problems of large amount of organic solvent used and difficult control in the two-step synthesis of 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine in the prior art, the purpose of the present invention is to provide a simple, green and low-cost one-step high-purity synthesis method of 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine.

[0010] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0011] A one-step synthesis method of 4,4',6,6'-tetrakis(hydrazino)hydrazine-1,3,5-triazine comprises the following steps:

[0012] The hydrazine hydrate ethylene glycol mixed solution is precooled and then added with cyanuric chloride ethylene glycol suspension, and after the reaction, filtered, washed and dried to obtain 4,4',6,6'-tetrakis(hydrazine)hydrazine-1,3,5-triazine.

[0013] A further improvement of the present invention is that the mass concentration of hydrazine hydrate is 80%.

[0014] A further improvement of the present invention is that the volume ratio of hydrazine hydrate to ethylene glycol in the hydrazine hydrate ethylene glycol mixed solution is 1:1 to 1:2.

[0015] A further improvement of the present invention is that the volume ratio of hydrazine hydrate to ethylene glycol in the hydrazine hydrate ethylene glycol solution is 1:1.5 to 1:2.

[0016] A further improvement of the present invention is that the precooling temperature is -20°C to -5°C.

[0017] A further improvement of the present invention is that the precooling temperature is -15°C to -10°C.

[0018] A further improvement of the present invention is that the usage ratio of cyanuric chloride glycol in the cyanuric chloride glycol suspension is 1g:2mL to 1g:3mL.

[0019] A further improvement of the present invention is that the usage ratio of cyanuric chloride glycol in the cyanuric chloride glycol suspension is 83 g:207 mL.

[0020] A further improvement of the present invention is that the reaction temperature is -15°C to 5°C and the reaction time is 2 to 4 hours.

[0021] A further improvement of the present invention is that the temperature is -10°C to 0°C and the reaction time is 3 to 4 hours.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows: the present invention uses cyanuric chloride as a raw material, ethylene glycol as a dispersant and a buffer, and the other reagents involved are all common cheap chemical raw materials. 4,4',6,6'-tetra (hydrazine) hydrazine-1,3,5-triazine is synthesized simply and efficiently by a one-step method. The compound can be further used to produce high-nitrogen energetic compounds 4,4',6,6'-tetra (azido) hydrazine-1,3,5-triazine and 4,4',6,6'-tetra (azido) azo-1,3,5-triazine. Compared with the synthesis method of the substance in the prior art, the one-step reaction step of the present method is simple and direct, and the existing two-step synthesis method is converted into a one-step reaction, which can efficiently prepare a high-purity target compound with a high yield. At the same time, the synthesis process no longer involves organic solvents such as tetrahydrofuran and acetonitrile, and ethylene glycol is used as a dispersant and a buffer, the reaction is easy to control, the process is relatively green and environmentally friendly, and the subsequent treatment is simple. In addition, the addition of ethylene glycol changes the existing direct feeding method of cyanuric chloride solid powder, realizes rapid and continuous flow feeding, and is easier to industrialize. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is the synthetic route map in the literature;

[0024] Figure 2 is the synthetic route diagram of the present invention;

[0025] Figure 3 is the infrared spectrum of 4,4',6,6'-tetrakis(hydrazino)hydrazine-1,3,5-triazine of Example 1;

[0026] Figure 4 This is the DSC chart of 4,4',6,6'-tetrakis(hydrazino)hydrazine-1,3,5-triazine of Example 1. DETAILED DESCRIPTION

[0027] In order to facilitate the understanding of the present invention, the present invention will be described more fully below with reference to the relevant drawings. The preferred embodiments of the present invention are given in the drawings. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thoroughly and comprehensively understood.

[0028] The invention provides a one-step synthesis method of 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine. Cyanuric chloride and hydrazine hydrate are used as raw materials, ethylene glycol is used as a dispersant and a buffer, and 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine is synthesized in a one-step method with high yield.

[0029] Specifically, the synthetic route is as follows Figure 2 As shown, the synthesis method of the present invention is: placing a mixed solution of hydrazine hydrate and ethylene glycol in a reactor and precooling it at -20°C to -5°C, then adding a cyanuric chloride glycol suspension, reacting at a set temperature for a certain time, filtering, washing, and drying to obtain high-purity 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine.

[0030] Wherein, the volume ratio of the hydrazine hydrate (mass concentration 80%) and ethylene glycol is 1:1 to 1:2.

[0031] The material-liquid ratio (g / mL) of the cyanuric chloride-ethylene glycol suspension is 1:2-1:3, that is, the ratio of cyanuric chloride to ethylene glycol is 1g:2mL-1g:3mL, and the molar ratio of hydrazine hydrate to cyanuric chloride is 1:4-1:6.

[0032] The reaction temperature is -15°C to 5°C, and the reaction time is 2 to 4 hours.

[0033] The cyanuric chloride in the present invention is also known as cyanuric chloride. Among its downstream synthetic products, pesticides occupy the vast majority of the consumer market. As an important chemical raw material for pesticides, dyes, and fluorescent agents, it is rarely used in the manufacturing field of high-nitrogen energetic compounds. The present invention uses cyanuric chloride as a raw material, and the other reagents involved are all common chemical raw materials. 4,4',6,6'-tetra (hydrazine) hydrazine-1,3,5-triazine is directly synthesized by a simple one-step method. The substance can be used as an important intermediate for high-nitrogen energetic compounds. Compared with the previous two-step synthesis method, the present method has a simple synthesis route, mild conditions, and easy-to-obtain raw materials. It avoids the use of organic solvents such as tetrahydrofuran and acetonitrile, has low cost, and is green and environmentally friendly. In addition, the feeding method of direct feeding of solid powder in the existing process is converted into liquid stream feeding, which is more conducive to industrial production and expanding its scope of application.

[0034] The following are specific embodiments to further illustrate the technical solutions of the present invention.

[0035] Example 1

[0036] 0.1 mol hydrazine hydrate (125 ml) and 187.5 ml ethylene glycol mixed solution were placed in a reactor and precooled at -15°C. 0.45 mol (83.0 g) cyanuric chloride was added to 207 ml ethylene glycol solution and stirred until a uniform suspension was formed. The cyanuric chloride ethylene glycol suspension was added to the precooled mixed solution, stirred at -10°C for 3.5 hours, filtered, washed and dried to obtain 65.6 g of white 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine with a yield of 94%.

[0037] IR(KBr)(cm -1 ): 3271(s), 2939(w), 1554(w), 1508(s), 1431(w), 1404(m), 1348(w), 1265(w), 1205(m), 1125(m), 1070(s), 933(s), 837(w), 798(s), 663(w), 623(m), 582(m), 457(m). C, H and N were determined by elemental analyzer (theoretical values ​​in brackets): C: 23.31(23.23), N: 70.10(72.23).

[0038] Figure 3 The infrared spectrum of 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine is shown in Figure 3271. -1 The characteristic peak at 2939cm is the stretching vibration peak of the NH bond on the triazine ring. -1 The characteristic peak at 1508cm is the stretching vibration peak of NH on -NH-NH2. -1 The characteristic peak at 1404 cm is the stretching vibration peak of the triazine ring skeleton. -1 The characteristic peak at 1070cm is the CN stretching vibration absorption peak. -1 The characteristic peak at is the stretching vibration peak of the NN bond.

[0039] Thermal decomposition performance test:

[0040] The 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine synthesized by the method of Example 1 was subjected to DSC measurement under the conditions of a nitrogen flow rate of 30 ml / min and a heating rate of 10°C / min, and the following was obtained: Figure 4 The results are shown. Figure 4 It can be seen that the thermal decomposition peak temperature of 4,4',6,6'-tetrakis(hydrazino)hydrazine-1,3,5-triazine is 301.6°C, which has good thermal stability.

[0041] Example 2

[0042] 0.1 mol hydrazine hydrate (125 ml) and 125 ml ethylene glycol mixed solution were placed in a reactor and precooled at -15°C. 0.45 mol (83.0 g) cyanuric chloride was added to 163 ml ethylene glycol solution and stirred until a uniform suspension was formed. The cyanuric chloride ethylene glycol suspension was added to the precooled mixed solution, stirred at -10°C for 3.5 hours, filtered, washed and dried to obtain 57.2 g of white 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine with a yield of 82%.

[0043] IR(KBr)(cm -1 ): 3233(s), 2899(w), 1513(w), 1466(s), 1402(w), 1368(m), 1309(w), 1255(w), 1203(m), 1105(m), 1039(s), 923(s), 817(w), 804(s), 643(w), 609(m), 563(m), 441(m). C, H, and N were determined by an elemental analyzer (theoretical values ​​in brackets): C: 23.39 (23.43), N: 71.16 (70.83).

[0044] Example 3

[0045] 0.1 mol hydrazine hydrate (125 ml) and 250 ml ethylene glycol mixed solution were placed in a reactor and precooled at -15°C. 0.45 mol (83.0 g) cyanuric chloride was added to 249 ml ethylene glycol solution and stirred until a uniform suspension was formed. The cyanuric chloride ethylene glycol suspension was added to the precooled mixed solution, stirred at -10°C for 3.5 hours, filtered, washed and dried to obtain 61.4 g of white 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine with a yield of 88%.

[0046] Example 4

[0047] 0.1 mol hydrazine hydrate (125 ml) and 187.5 ml ethylene glycol mixed solution were placed in a reactor and precooled at -15°C. 0.50 mol (92.2 g) cyanuric chloride was added to 230 ml ethylene glycol solution and stirred until a uniform suspension was formed. The cyanuric chloride ethylene glycol suspension was added to the precooled mixed solution, stirred at -10°C for 3.5 hours, filtered, washed and dried to obtain 67.48 g of white 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine with a yield of 87%.

[0048] Example 5

[0049] 0.1 mol of hydrazine hydrate (125 ml) and 187.5 ml of ethylene glycol mixed solution were placed in a reactor and precooled at -15°C. 0.40 mol (73.76 g) of cyanuric chloride was added to 184 ml of ethylene glycol solution and stirred until a uniform suspension was formed. The cyanuric chloride ethylene glycol suspension was added to the precooled mixed solution, stirred at -10°C for 3.5 hours, filtered, washed, and dried to obtain 52.1 g of white 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine with a yield of 84%.

[0050] Example 6

[0051] 0.1 mol of hydrazine hydrate (125 ml) and 187.5 ml of ethylene glycol mixed solution were placed in a reactor and precooled at -15°C. 0.6 mol (110.65 g) of cyanuric chloride was added to 276.6 ml of ethylene glycol solution and stirred until a uniform suspension was formed. The cyanuric chloride ethylene glycol suspension was added to the precooled mixed solution, stirred at -10°C for 3.5 hours, filtered, washed, and dried to obtain 75.4 g of white 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine with a yield of 81%.

[0052] Example 7

[0053] 0.1 mol hydrazine hydrate (125 ml) and 187.5 ml ethylene glycol mixed solution were placed in a reactor and precooled at -20°C. 0.45 mol (83.0 g) cyanuric chloride was added to 207 ml ethylene glycol solution and stirred until a uniform suspension was formed. The cyanuric chloride ethylene glycol suspension was added to the precooled mixed solution, stirred at -10°C for 3.5 hours, filtered, washed and dried to obtain 63.5 g of white 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine with a yield of 91%.

[0054] Example 8

[0055] 0.1 mol hydrazine hydrate (125 ml) and 187.5 ml ethylene glycol mixed solution were placed in a reactor and precooled at -5°C. 0.45 mol (83.0 g) cyanuric chloride was added to 207 ml ethylene glycol solution and stirred until a uniform suspension was formed. The cyanuric chloride ethylene glycol suspension was added to the precooled mixed solution, stirred at -10°C for 3.5 hours, filtered, washed and dried to obtain 58.6 g of white 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine with a yield of 84%.

[0056] Example 9

[0057] 0.1 mol hydrazine hydrate (125 ml) and 187.5 ml ethylene glycol mixed solution were placed in a reactor and precooled at -15°C. 0.45 mol (83.0 g) cyanuric chloride was added to 207 ml ethylene glycol solution and stirred until a uniform suspension was formed. The cyanuric chloride ethylene glycol suspension was added to the precooled mixed solution, stirred at -15°C for 3.5 hours, filtered, washed and dried to obtain 64.2 g of white 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine with a yield of 92%.

[0058] Example 10

[0059] 0.1 mol of hydrazine hydrate (125 ml) and 187.5 ml of ethylene glycol mixed solution were placed in a reactor and precooled at -15°C. 0.45 mol (83.0 g) of cyanuric chloride was added to 207 ml of ethylene glycol solution and stirred until a uniform suspension was formed. The cyanuric chloride ethylene glycol suspension was added to the precooled mixed solution, stirred at -5°C for 3.5 hours, filtered, washed, and dried to obtain 62.1 g of white 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine with a yield of 89%.

[0060] Embodiment 11

[0061] 0.1 mol hydrazine hydrate (125 ml) and 187.5 ml ethylene glycol mixed solution were placed in a reactor and precooled at -15°C. 0.45 mol (83.0 g) cyanuric chloride was added to 207 ml ethylene glycol solution and stirred until a uniform suspension was formed. The cyanuric chloride ethylene glycol suspension was added to the precooled mixed solution, stirred at -10°C for 2 hours, filtered, washed and dried to obtain 56.5 g of white 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine with a yield of 81%.

[0062] Example 12

[0063] 0.1 mol hydrazine hydrate (125 ml) and 187.5 ml ethylene glycol mixed solution were placed in a reactor and precooled at -15°C. 0.45 mol (83.0 g) cyanuric chloride was added to 207 ml ethylene glycol solution and stirred until a uniform suspension was formed. The cyanuric chloride ethylene glycol suspension was added to the precooled mixed solution, stirred at -10°C for 3 hours, filtered, washed and dried to obtain 60.0 g of white 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine with a yield of 86%.

[0064] Example 13

[0065] 0.1 mol hydrazine hydrate (125 ml) and 187.5 ml ethylene glycol mixed solution were placed in a reactor and precooled at -15°C. 0.45 mol (83.0 g) cyanuric chloride was added to 207 ml ethylene glycol solution and stirred until a uniform suspension was formed. The cyanuric chloride ethylene glycol suspension was added to the precooled mixed solution, stirred at -10°C for 4 hours, filtered, washed and dried to obtain 64.9 g of white 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine with a yield of 93%.

[0066] Embodiment 14

[0067] Place 93.75 ml of hydrazine hydrate and 187.5 ml of ethylene glycol mixed solution in a reactor and precool at -10°C. Add 0.45 mol (83.0 g) of cyanuric chloride to 207 ml of ethylene glycol solution and stir until a uniform suspension is formed. Add the cyanuric chloride ethylene glycol suspension to the precooled mixed solution, stir and react at 0°C for 3 hours, filter, wash and dry to obtain 57.2 g of white 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine with a yield of 82%.

[0068] Embodiment 15

[0069] Place 187.5 ml of hydrazine hydrate and 187.5 ml of ethylene glycol mixed solution in a reactor and precool at -5°C. Add 0.45 mol (83.0 g) of cyanuric chloride to 207 ml of ethylene glycol solution and stir until a uniform suspension is formed. Add the cyanuric chloride ethylene glycol suspension to the precooled mixed solution, and a large amount of yellow solid will immediately appear in the solution. React at 5°C for 4 hours, filter, wash and dry to obtain 60.0 g of white 4,4',6,6'-tetra(hydrazino)hydrazine-1,3,5-triazine with a yield of 86%.

[0070] Compared with the existing synthesis methods, this synthesis method is simple, greatly reduces the amount of organic solvents, and is relatively green and environmentally friendly. At the same time, the raw materials are cheap and available, the reaction conditions are mild, and it is easy to industrialize.

[0071] The above description is only for the best embodiment of the present invention, but it should not be understood as limiting the claims. The present invention is not limited to the above embodiments, and its specific structure is allowed to be changed. However, all changes made within the protection scope of the independent claims of the present invention are within the protection scope of the present invention.

[0072] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

Claims

1. A one-step synthesis method of 4,4',6,6'-tetrakis(hydrazino)hydrazine-1,3,5-triazine, characterized in that: The following steps are involved: The hydrazine hydrate ethylene glycol mixed solution is precooled and then added with cyanuric chloride ethylene glycol suspension, and after the reaction, filtered, washed and dried to obtain 4,4',6,6'-tetrakis(hydrazine)hydrazine-1,3,5-triazine.

2. The one-step synthesis method of 4,4',6,6'-tetrakis(hydrazino)hydrazine-1,3,5-triazine according to claim 1, characterized in that: The mass concentration of hydrazine hydrate is 80%.

3. The one-step synthesis method of 4,4',6,6'-tetrakis(hydrazino)hydrazine-1,3,5-triazine according to claim 1 or 2, characterized in that: The volume ratio of hydrazine hydrate to ethylene glycol in the hydrazine hydrate ethylene glycol mixed solution is 1:1 to 1:

2.

4. The one-step synthesis method of 4,4',6,6'-tetrakis(hydrazino)hydrazine-1,3,5-triazine according to claim 1, characterized in that: The volume ratio of hydrazine hydrate to ethylene glycol in the hydrazine hydrate ethylene glycol solution is 1:1.5 to 1:

2.

5. The one-step synthesis method of 4,4',6,6'-tetrakis(hydrazino)hydrazine-1,3,5-triazine according to claim 1, characterized in that: The precooling temperature is -20℃~-5℃.

6. The one-step synthesis method of 4,4',6,6'-tetrakis(hydrazino)hydrazine-1,3,5-triazine according to claim 1, characterized in that: The precooling temperature is -15℃~-10℃.

7. The one-step synthesis method of 4,4',6,6'-tetrakis(hydrazino)hydrazine-1,3,5-triazine according to claim 1, characterized in that: The dosage ratio of cyanuric chloride glycol in the cyanuric chloride glycol suspension is 1g:2mL to 1g:3mL.

8. The one-step synthesis method of 4,4',6,6'-tetrakis(hydrazino)hydrazine-1,3,5-triazine according to claim 1, characterized in that: The dosage ratio of cyanuric chloride in the cyanuric chloride suspension is 83g:207mL.

9. The one-step synthesis method of 4,4',6,6'-tetrakis(hydrazino)hydrazine-1,3,5-triazine according to claim 1, characterized in that: The reaction temperature is -15°C to 5°C, and the reaction time is 2 to 4 hours.

10. The one-step synthesis method of 4,4',6,6'-tetrakis(hydrazino)hydrazine-1,3,5-triazine according to claim 1, characterized in that: -10℃~0℃, reaction time is 3~4h.

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