CN112239430B - Synthesis method of azinyl triazine high-nitrogen energetic compound - Google Patents
Synthesis method of azinyl triazine high-nitrogen energetic compound Download PDFInfo
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Abstract
A method for synthesizing azido triazine high-nitrogen energetic compound is characterized in that trihydrazino-s-triazine is used as a raw material to synthesize 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine by a one-step method. Dispersing trihydrazino-s-triazine in an acidic aqueous solution, adding a nitrite aqueous solution, reacting for a certain time at a set temperature, filtering, washing, and drying in vacuum to obtain the azidotriazine high-nitrogen energetic compound 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine. The synthesis method is simple, does not relate to organic solvents, and is green and environment-friendly. Meanwhile, the raw materials are cheap and available, the reaction conditions are mild, and the industrial production is easy to realize.
Description
Technical Field
The invention belongs to the field of energetic materials, and particularly relates to a synthesis method of a high-nitrogen energetic compound of triazotriazine.
Background
High-nitrogen energetic compounds become an important direction for the research and development of novel green energetic materials due to high nitrogen content and large enthalpy of formation, and azide triazine high-nitrogen compounds are an important class of the high-nitrogen energetic compounds. In 2004, 4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine was synthesized by Huynh m.h. et al, los alamos national laboratory, usa, for the first time by three-step reaction using cyanuric chloride as a raw material, and further, 4 ', 6, 6' -tetra (azido) azo-1,3,5-triazine (Scheme 1), which is a compound with higher nitrogen content, was synthesized (see fig. 1) [ reference 1 and 2 ]. Subsequently, the domestic scholars have also made relevant studies on the synthesis reaction and the properties of the corresponding high nitrogen compounds [ references 3 and 4 ]. However, in summary, the synthesis of 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine is one of the key. Although the yield reported by the three-step synthesis reaction is relatively high, the reaction is severe, the reaction conditions are relatively harsh, and a large amount of organic solvents such as tetrahydrofuran, acetonitrile and the like are required, so that the synthesis of 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine is remarkably limited, and further 4,4 ', 6, 6' -tetra (azido) azo-1,3,5-triazine with higher nitrogen content is synthesized, and the method becomes a barrier for industrial application.
Reference documents:
[1]Loew,P.,Weis,C.Azo-1,3,5-triazines.Journal of Heterocyclic Chemistry,1976,13(4):829-833.
[2]Huynh M.H.,Hiskey M.A.,Hartline E.L.,Montoya D.P.,Gilardi R.Polyazido high-nitrogen compounds:hydrazo and azo-1,3,5-triazine.Angew.Chem.2004,116:5032-5036.
[3]Li X.T.,Li S.H.,Pang S.P.,Yu Y.Z.,Luo Y.J.Chinese Chemical Letter,2007,18:1037-1039.
[4] li Xiaotong, Poncin, Yong faithful, Luo Shi Jun, research on the synthesis of 4,4 ', 6, 6' -tetraazidoazo-1, 3,5-triazine, energetic materials, 2007,115(5):485 and 489.
Disclosure of Invention
The invention aims to provide a simple synthesis method of an azinyl triazine high-nitrogen energetic compound.
In order to realize the purpose, the technical scheme adopted by the method is as follows:
dispersing trihydrazino-s-triazine in an acidic aqueous solution, adding a nitrite aqueous solution, and reacting for a certain time at a set temperature to obtain the azidotriazine high-nitrogen energetic compound 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine.
The invention is further improved in that the acidic solution is an aqueous solution of nitric acid, hydrochloric acid, sulfuric acid or acetic acid.
The invention is further improved in that the concentration of the acidic solution is 0.15 mol/L-0.25 mol/L.
In a further development of the invention, the nitrite is sodium nitrite or potassium nitrite.
The invention further improves that the molar ratio of the trihydrazino-s-triazine to the acid to the nitrite is 1: (3-5): (3-6).
The invention is further improved in that the reaction temperature is 0-80 ℃.
The invention is further improved in that the reaction time is 40 min-120 min.
Compared with the prior art, the invention has the following beneficial effects: the invention takes trihydrazino-s-triazine as a raw material, related other reagents are common chemical reagents, the azido triazine high-nitrogen energetic compound 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine is simply synthesized by a one-step method, the nitrogen mass content of the compound is 79.09%, and the compound can be used as the azido triazine high-nitrogen energetic material and intermediates for further synthesizing other derivatives. Compared with the method for synthesizing the substance in the prior art, the method has simpler reaction steps, and can prepare the target product with high yield by one-step reaction. Organic solvent is not involved in the synthesis process, and the method is green and environment-friendly. Meanwhile, the raw materials are cheap and available, the reaction conditions are mild, and the industrial production is easy to realize.
Drawings
FIG. 1 is a synthetic route diagram in the literature;
FIG. 2 is a nuclear magnetic H spectrum of 4,4 ', 6, 6' -tetrakis (azido) hydrazine-1, 3,5-triazine of example 1;
FIG. 3 is a crystal structure diagram of 4,4 ', 6, 6' -tetrakis (azido) hydrazine-1, 3,5-triazine of example 2;
FIG. 4 is a DSC of 4,4 ', 6, 6' -tetrakis (azido) hydrazine-1, 3,5-triazine of example 2;
FIG. 5 is a synthetic route diagram of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The invention provides a novel synthesis method, which takes trihydrazino-s-triazine as a raw material to synthesize 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine with high yield by a one-step method.
Specifically, the synthetic route is shown in fig. 5, and the synthetic method of the invention comprises the following steps: dispersing trihydrazino-s-triazine in an acidic aqueous solution, adding a nitrite aqueous solution, reacting for a certain time at a set temperature, filtering, washing, and drying in vacuum to obtain the azidotriazine high-nitrogen energetic compound 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine.
Wherein the acidic aqueous solution is dilute nitric acid, hydrochloric acid, sulfuric acid or acetic acid aqueous solution. The concentration of the acid solution is 0.15 mol/L-0.25 mol/L.
The nitrite is sodium nitrite or potassium nitrite.
The molar ratio of the trihydrazino-s-triazine to the acid to the nitrite is 1: 3-5: 3 to 6.
The reaction temperature is 0-80 ℃, and the reaction time is 40-120 min.
The synthesis of high-nitrogen compounds by taking oxazine compounds as raw materials is a common method for synthesizing novel high-energy energetic materials, and the trihydrazino s-triazine as a common chemical raw material with stable properties is rarely applied to the field of energetic materials. The invention takes trihydrazino-s-triazine as a raw material, related other reagents are common chemical reagents, the azido triazine high-nitrogen energetic compound 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine is simply synthesized by a one-step method, the nitrogen mass content of the compound is 79.09%, and the compound can be used as the azido triazine high-nitrogen energetic material and intermediates for further synthesizing other derivatives. Compared with the prior method for synthesizing the substance, the method has the advantages of simpler reaction steps, milder reaction conditions, cheap and commercially available reaction raw materials, no organic solvent and environmental protection.
The following are specific examples to further illustrate the technical aspects of the present invention.
Example 1
Dispersing trihydrazino-s-triazine in an acidic aqueous solution, slowly adding a nitrite aqueous solution, reacting for a certain time at a set temperature, filtering, washing, and drying in vacuum to obtain the azidotriazine high-nitrogen energetic compound 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine.
Dispersing 0.1mol (17.1g) of trihydrazino-s-triazine into 500mL of aqueous solution containing glacial acetic acid (0.3mol), adding aqueous solution containing 0.3mol (20.7g) of sodium nitrite at 5 ℃, reacting for 60min, filtering, washing and drying in vacuum to obtain the azidotriazine high-nitrogen energetic compound 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine 15.3g, wherein the yield is 86.3%.
FIG. 2 is the nuclear magnetic H spectrum of 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine of the present invention. Referring to fig. 2, the corresponding structural characterization results are as follows:1H NMR(DMSO-d6400MHz, delta) 10.57 ppm. The results are consistent with the results of the synthesis study of the document [ Li Xiaotong, Pangxiping, Yong faithful, Roche, 4 ', 6, 6' -tetraazidoazo-1, 3,5-triazine as the high-nitrogen compound, 2007,115(5): 485-.
Example 2
0.01mol of 4,4 ', 6, 6' -tetrakis (azido) hydrazine-1, 3,5-triazine synthesized as in example 1 was dissolved in 20mL of acetone with water 1: 1, standing at room temperature for 4-5 days to obtain 4,4 ', 6, 6'Yellow crystals of tetrakis (azido) hydrazine-1, 3,5-triazine. FIG. 2 is a crystal structure diagram of 4,4 ', 6, 6' -tetrakis (azido) hydrazine-1, 3,5-triazine in example 2. Referring to FIG. 3, the crystal is triclinic, space group P-1, unit cell parameter as measured by X-ray diffraction
Z＝2，μ＝0.131mm-1，F(000)＝356，Dc＝1.665g·cm-3，R10.0871 and wR20.2607. Consistent with the results obtained in the literature [ Huynh M.H., Hiskey M.A., Hartlene E.L., Montoya D.P., Gilardi R.Polyazido high-nitrobenzene compounds: hydrazo and azo-1,3,5-triazine Angew. chem.2004,116: 5032-.
FIG. 4 is a DSC of 4,4 ', 6, 6' -tetrakis (azido) hydrazine-1, 3,5-triazine from example 2. As can be seen from FIG. 4, the compound is thermally stable.
Example 3
Dispersing 0.1mol (17.1g) of trihydrazino-s-triazine into 500mL of aqueous solution containing dilute sulfuric acid (0.3mol), adding sodium nitrite solution containing 0.3mol (20.7g) of sodium nitrite at 5 ℃, reacting for 60min, filtering, washing and drying in vacuum to obtain the azidotriazine high-nitrogen energetic compound 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine 11.7g, wherein the yield is 66.3%.
Example 4
Dispersing 0.1mol (17.1g) of trihydrazino-s-triazine into 500mL of aqueous solution containing dilute hydrochloric acid (0.3mol), adding sodium nitrite solution containing 0.3mol (20.7g) of sodium nitrite at 5 ℃, reacting for 60min, filtering, washing and drying in vacuum to obtain the azidotriazine high-nitrogen energetic compound 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine 10.8g, with the yield of 61.2%.
Example 5
Dispersing 0.1mol (17.1g) of trihydrazino-s-triazine into 500mL of aqueous solution containing dilute nitric acid (0.3mol), adding sodium nitrite solution containing 0.3mol (20.7g) of sodium nitrite at 5 ℃, reacting for 60min, filtering, washing, and drying in vacuum to obtain the azidotriazine high-nitrogen energetic compound 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine 10.7g, wherein the yield is 60.7%.
Example 6
Dispersing 0.1mol (17.1g) of trihydrazino-s-triazine into 500mL of aqueous solution containing glacial acetic acid (0.3mol), adding sodium nitrite solution containing 0.3mol (20.7g) of sodium nitrite at 0 ℃, reacting for 60min, filtering, washing and drying in vacuum to obtain the azidotriazine high-nitrogen energetic compound 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine 14.2g, wherein the yield is 80.1%.
Example 7
Dispersing 0.1mol (17.1g) of trihydrazino-s-triazine into 500mL of aqueous solution containing glacial acetic acid (0.3mol), adding sodium nitrite solution containing 0.3mol (20.7g) of sodium nitrite at 30 ℃, reacting for 60min, filtering, washing and drying in vacuum to obtain 13.4g of azido triazine high-nitrogen energetic compound 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine with the yield of 75.5%.
Example 8
Dispersing 0.1mol (17.1g) of trihydrazino-s-triazine into 500mL of aqueous solution containing glacial acetic acid (0.3mol), adding sodium nitrite solution containing 0.3mol (20.7g) of sodium nitrite at 80 ℃, reacting for 60min, filtering, washing and drying in vacuum to obtain 12.8g of azido triazine high-nitrogen energetic compound 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine with the yield of 72.5%.
Example 9
Dispersing 0.1mol (17.1g) of trihydrazino-s-triazine into 500mL of aqueous solution containing glacial acetic acid (0.3mol), adding sodium nitrite solution containing 0.3mol (20.7g) of sodium nitrite at 5 ℃, reacting for 40min, filtering, washing and drying in vacuum to obtain 13.8g of azido triazine high-nitrogen energetic compound 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine with the yield of 77.7%.
Example 10
Dispersing 0.1mol (17.1g) of trihydrazino-s-triazine into 500mL of aqueous solution containing glacial acetic acid (0.3mol), adding sodium nitrite solution containing 0.3mol (20.7g) of sodium nitrite at 5 ℃, reacting for 120min, filtering, washing and drying in vacuum to obtain 13.2g of azidotriazine high-nitrogen energetic compound 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine with the yield of 74.5%.
Example 11
Dispersing 0.1mol (17.1g) of trihydrazino-s-triazine into 500mL of aqueous solution containing glacial acetic acid (0.3mol), adding potassium nitrite solution containing 0.3mol (25.5g) of sodium nitrite at 5 ℃, reacting for 60min, filtering, washing and drying in vacuum to obtain the azidotriazine high-nitrogen energetic compound 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine 14.8g, wherein the yield is 83.6%.
Example 12
Dispersing 0.1mol (17.1g) of trihydrazino-s-triazine into 500mL of aqueous solution containing glacial acetic acid (0.4mol), adding 0.4mol (27.6g) of sodium nitrite solution at 5 ℃, reacting for 60min, filtering, washing and drying in vacuum to obtain the azidotriazine high-nitrogen energetic compound 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine 14.3g with the yield of 81.7%.
Example 13
Dispersing 0.1mol (17.1g) of trihydrazino-s-triazine into 500mL of aqueous solution containing glacial acetic acid (0.5mol), adding aqueous solution containing 0.6mol (41.7g) of sodium nitrite at 5 ℃, reacting for 60min, filtering, washing and drying in vacuum to obtain the azidotriazine high-nitrogen energetic compound 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine 14.5g with the yield of 82.1%.
Claims (5)
1. A method for synthesizing azino triazine high-nitrogen energetic compound is characterized in that trihydrazino-s-triazine is dispersed in an acidic aqueous solution, then a nitrite aqueous solution is added, and reaction is carried out for a certain time at a set temperature to obtain 4,4 ', 6, 6' -tetra (azido) hydrazine-1, 3,5-triazine as the azino triazine high-nitrogen energetic compound;
the acidic aqueous solution is nitric acid, hydrochloric acid, sulfuric acid or acetic acid aqueous solution; the reaction temperature is 0-80 ℃.
2. The synthesis method of azinyl triazine high-nitrogen energetic compound as claimed in claim 1, wherein the concentration of the acidic aqueous solution is 0.15-0.25 mol/L.
3. The method for synthesizing azidotriazine high-nitrogen energetic compound according to claim 1, wherein the nitrite is sodium nitrite or potassium nitrite.
4. The method for synthesizing azino-triazine high-nitrogen energetic compound according to claim 1, wherein the molar ratio of trihydrazino-s-triazine, acid and nitrite is 1: (3-5): (3-6).
5. The synthesis method of azinyl triazine high-nitrogen energetic compound as claimed in claim 1, wherein the reaction time is 40-120 min.
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