CN109096215A - Rich nitrogen energetic material 3- amino -3 '-nitramino -5,5 '-connection -1,2,4- triazole and preparation method thereof - Google Patents
Rich nitrogen energetic material 3- amino -3 '-nitramino -5,5 '-connection -1,2,4- triazole and preparation method thereof Download PDFInfo
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- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention discloses a kind of rich nitrogen energetic material 3- amino -3'- nitraminos -5,5'- to join -1,2,4- triazoles and preparation method thereof, which is to be synthesized for the first time.Logical 3- amino -3'- nitramino -5,5'- joins -1,2,4- triazoles and finds that it is a kind of with good thermal stability after tested, meets the insensitive energetic material of insensitive energetic material requirement, impact sensitivity 80J, friction sensitivity 360N.In view of the superperformance of the compound, preparation method is very important.The present invention is directed to the compound, have developed the synthetic route of reliable, cheap suitable amplification, the raw material 5- amino -1 being easy to get from commercialization, 2,4- triazolyl -3- formic acid sets out, and obtains target product by the hydrazinolysis reaction of the esterification of sulphuric acid catalysis, hydrazine hydrate and the ring closure reaction of N- methyl-N nitro-N nitrosoguanidine, used raw material is simple and easy to get, cheap, overall reaction yield can be up to 49%.
Description
Technical field
The invention belongs to energetic material fields, specifically related to a kind of novel insensitive rich nitrogen energetic material 3- amino -3'-
Nitramino -5,5'- joins -1,2,4- triazoles and preparation method thereof, and the present invention will have in green priming medicine and high explosive
Preferable application prospect.
Background technique
The energy of azotic heterocyclic compound comes not only from the tensile strain of framework ring, and because it contains high-energy chemistry key such as
N-N, N=N, C-N, C=N and N-O key etc. and there is the higher enthalpy of formation, while its combustion product N2 environmental pollution is smaller；
So exploring and research and develop azole high energy material substitutes traditional energy-containing compound, it has also become research hotspot, last decade are competitively reported
Road.
Using triazole and tetrazolium as the azotic heterocyclic compound of representative, it is that synthesizing new high energy material probes into hot spot, because
They usually have the characteristics that higher generation heat, higher density, nitrogen content are high and to outside stimulus hyposensitivity, are expected to apply to
In main explosive and priming.For tetrazolium, the enthalpy of formation of 1,2,4- triazole is although lower, but has in skeleton less
Chain nitrogen-atoms, keep it more stable to outside stimulus, and two in skeleton carbon atom is symmetrical, space bit after substitutionization
Hinder it is small, so have more abundant derivatization replace so that its derive species have more diversity, more suitable for high energy material
Exploitation.Such as 5- amino -3- nitro -1,2,4- triazole (ANTA), 3- nitro -5- triazolone (NTO) and azo-compound 5,5'-
Dinitro -3,3'- azo -1,2,4- triazole (DNAT), these compound decomposition temperatures are greater than 200 DEG C, show 1,2,4- triazoles
Class compound all has good thermal stability and safety.
Triazole bis-heterocyclic compounds contain more nitrogen compared to triazole list heterocyclic ligand, compare tetrazolium list heterocyclic ligand knot
Structure is more symmetrical, nitrogens containing lone pair electrons are more evenly distributed, the high energy energy-containing compound of stable structure, competing in recent years
Mutually research report.The synthesis azo bound 5 such as L.Naud, 5'- dinitro -3,3'- azo -1,2,4- triazole (DNAT),
Its density is 1.88gcm-3, enthalpy of formation 407kJmol-1.With the 1 of azo bridging, 2,4- triazole compounds are compared, C-C
Double-the 1 of key connection, 2,4- triazoles have similar energy properties, and D.E.L.Metelkina etc. is to 5,5'- dinitro imino group-
3,3'- bis- -1, the different route of synthesis of 2,4- triazoles (H2DNABT) have made intensive studies, density 1.8gcm-3, raw
Cheng Han be+405kJmol-1, explosion velocity 8355ms-1, thermodynamic property with containing energy performance and DNAT it is suitable.So connection three
Azoles have synthesis green non-pollution, safety, high energy energetic material potential quality.
Therefore, it is amino and nitramino that the present invention, which chooses the group containing energy, determines step simplicity, mild condition, a mesh
Mark the asymmetric novel connection triazole energy-containing compound 3- amino -3'- nitramino -5,5'- connection -1,2,4- three of synthesis of product yield high
Azoles method, by the characterization and heat analysis to its structure, the potential value studied and assess it as energetic material, this this be this
First synthetic route of compound, has no relevant report before.
Summary of the invention
The object of the present invention is to provide a kind of novel energetic material 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazoles
Preparation method, for novel energetic material synthesis and amplification research new method is provided.
In order to achieve the above objectives, an embodiment of the present invention adopts the following technical solutions:
The present invention provides a kind of rich nitrogen energetic material 3- amino -3'- nitraminos -5,5'- to join -1,2,4- triazoles, it
Structural formula is as follows:
The present invention also provides the preparation sides of rich nitrogen energetic material 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole
Method, it the following steps are included:
(1) synthesis of 3- amino -1H-1,2,4- triazole -5- carboxylate methyl ester
Anhydrous alcohols solvent and 3- amino -1H-1 are taken, -5 carboxylic acid of 2,4- triazole, stirring makes 3- amino -1H-1, and 2,4- tri-
- 5 carboxylic acid of nitrogen azoles, which is suspended in anhydrous alcohols solvent, obtains reaction solution, and concentrated sulfuric acid catalyst is slowly added dropwise in reaction solution, rises
Temperature reflux at least 2h, then natural cooling, revolving remove partial solvent, and precipitation obtains 3- amino -1H-1,2,4- triazole -5- carboxylics
Acid esters sulfate precipitation；Distilled water is added to the precipitating, adjusting pH is 5-6, and suction filtration obtains white precipitate, washed with dehydrated alcohol
It washs, is dried to obtain 3- amino -1H-1,2,4- triazole -5- carboxylates；
(2) synthesis of 3- amino -1H-1,2,4- triazole -5- carbohydrazide
3- amino -1H-1 is taken, the hydrazine hydrate that hydrazine mass content is 80% is slowly added dropwise to it in 2,4- triazole -5- carboxylates,
It is stirred to react at room temperature overnight, suction filtration obtains white solid, dry obtained 3- amino -1H-1,2,4- triazole -5- carbohydrazides；
(3) synthesis of 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole
3- amino -1H-1 is taken, 2,4- triazole -5- carbohydrazides are simultaneously suspended in deionized water, take a certain amount of N- methyl-N- nitre
Base-N nitrosoguanidine (MNNG) is suspended in solvent, and the latter is slowly dropped in the former and obtains reaction solution, and it is anti-to be warming up to reflux
It answers, is cooled to 50 DEG C after the reaction was completed hereinafter, be then slowly added into KOH solution, then be warming up to back flow reaction, it is cold after the reaction was completed
It but is 3-4 with dilute acid for adjusting pH to room temperature, cool overnight filters and obtains yellow mercury oxide, washed, be dried to obtain with dehydrated alcohol
Yellow solid product 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole.
The rich nitrogen energetic material 3- amino -3'- nitramino -5,5'- joins in the preparation method of -1,2,4- triazoles, step
Suddenly the use ratio of -5 carboxylic acid of (1) described anhydrous alcohols solvent and 3- amino -1H-1,2,4- triazole is that the anhydrous alcohols of every 1L is molten
- 5 carboxylic acid of suspension 0.08-0.15mol3- amino -1H-1,2,4- triazole in agent.
The rich nitrogen energetic material 3- amino -3'- nitramino -5,5'- joins in the preparation method of -1,2,4- triazoles, step
Suddenly (1) described anhydrous alcohols solvent is anhydrous methanol or dehydrated alcohol, they are as esterifying agent.
The rich nitrogen energetic material 3- amino -3'- nitramino -5,5'- joins in the preparation method of -1,2,4- triazoles, step
Suddenly it is 50% smoke H2SO4 or 98% concentrated sulfuric acid, anhydrous alcohols described in every 1L that (1) described concentrated sulfuric acid catalyst, which is mass fraction,
Solvent is corresponding to use 0.065-0.075L concentrated sulfuric acid catalyst.Concentrated sulfuric acid catalyst is also dehydrating agent.
The rich nitrogen energetic material 3- amino -3'- nitramino -5,5'- joins in the preparation method of -1,2,4- triazoles, step
Suddenly the use ratio of (2) described 3- amino -1H-1,2,4- triazole -5- carboxylate and 80% hydrazine hydrate is every 1mol3- amino -
1H-1,2,4- triazole -5- carboxylate uses 80% hydrazine hydrate of 0.3-0.35L.
The rich nitrogen energetic material 3- amino -3'- nitramino -5,5'- joins in the preparation method of -1,2,4- triazoles, step
Suddenly (2) described 3- amino -1H-1,2,4- triazole -5- carboxylate is 3- amino -1H-1,2,4- triazole -5- carboxylate methyl ester and 3- ammonia
The mixture of any one or two kinds in base -1H-1,2,4- triazole -5- carboxylic acid, ethyl ester.
The rich nitrogen energetic material 3- amino -3'- nitramino -5,5'- joins in the preparation method of -1,2,4- triazoles, step
Suddenly (3) described 3- amino -1H-1,2,4- triazole -5- carbohydrazide and the molar ratio of the N- methyl N-nitro-N nitrosoguanidine are
4.9-5.2:1；The concentration of the KOH solution is 0.18-0.20g/mL, every to use 1molN- methyl N-nitro-N nitrosoguanidine
Then using KOH solution described in 0.5L.
The rich nitrogen energetic material 3- amino -3'- nitramino -5,5'- joins in the preparation method of -1,2,4- triazoles, step
Suddenly the time of the back flow reaction of (1) is 10-14h；The time of first time back flow reaction in step (3) be 1-3h, second time
The time of stream reaction is 2-4h.
The rich nitrogen energetic material 3- amino -3'- nitramino -5,5'- joins in the preparation method of -1,2,4- triazoles, step
Suddenly (3) described diluted acid is dust technology or dilute sulfuric acid；The solvent of suspension N- methyl N-nitro-N nitrosoguanidine is methanol or second
Alcohol.N- methyl N-nitro-N nitrosoguanidine is cyclization reagent.
3- amino -3'- nitramino -5,5'- prepared by the method for the present invention joins -1,2,4- triazole samples, after tested
It was found that it is a kind of with good thermal stability, meet the insensitive energetic material of insensitive energetic material requirement, shock sense
Spend 80J, friction sensitivity 360N.Therefore, in view of the superperformance of the compound, preparation method is very important.This hair
It is bright aiming at the compound, design and develop the synthetic route of a reliable, cheap suitable amplification.This method
The raw material 5- amino-1,2,4-triazole base -3- formic acid being easy to get from commercialization, by the esterification of sulphuric acid catalysis, hydration
The hydrazinolysis reaction of hydrazine and the ring closure reaction of N- methyl-N nitro-N nitrosoguanidine obtain target product.The route completes 3- for the first time
Amino -3'- nitramino -5,5'- joins the synthesis of -1,2,4- triazoles, and used raw material is simple and easy to get, cheap, overall reaction
Yield can be up to 49%.
Compared with prior art, the present invention at least has the advantages that 3- amino -3'- nitramino -5,5'- connection -1,
2,4- triazoles have good safety and detonation property, while possessing excellent free-running property, can be used as explosive, gunpowder and pushing away
Into the composition of agent, in high-energy insensitive ammunition with good application prospect.Preparation method process flow letter of the invention
Single, easy to operate, reaction condition is mild, and safety is good, and product quality is high.
Detailed description of the invention
Fig. 1 is the infrared spectrum of 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole.
Fig. 2 is the TG-DSC curve of 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Embodiment 1
(1) synthesis of 3- amino -1H-1,2,4- triazole -5- carboxylate methyl ester
Anhydrous methanol 90mL is added in 250mL three-necked bottle, takes 3- amino -1H-1, -5 carboxylic acid 12.8g of 2,4- triazole
(10mmol), stirring make it be suspended in anhydrous methanol, take 50% smoke H of 6mL2SO4It is slowly added dropwise in reaction solution, is warming up to 85 DEG C
Back flow reaction 12h, natural cooling, revolving remove part methanol, and precipitation obtains 3- amino -1H-1,2,4- triazole -5- carboxylate methyl esters
Sulfate precipitation.20mL distilled water is added to precipitating, with NaOH (5molL-1) adjusting pH be 5-6, suction filtration obtain white precipitate,
It is washed 2-3 times with dehydrated alcohol, is dried to obtain 3- amino -1H-1,2,4- triazole -5- carboxylate methyl esters (yield 73%).
(2) synthesis of 3- amino -1H-1,2,4- triazole -5- carbohydrazide
3- amino -1H-1,2,4- triazole -5- carboxylate methyl ester 4.26g (30mmol) are added into 50mL single port bottle, slowly drip
Add 80% hydrazine hydrate 9.6mL, be stirred to react 14h at room temperature, filters and obtain white solid, dry obtained 3- amino -1H-1,2,4-
Triazole -5- carbohydrazide (yield 90%).
(3) synthesis of 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole
3- amino -1H-1,2,4- triazole -5- carbohydrazide 2.1g (14.8mmol) is added into 100mL there-necked flask and suspends
In 20mL deionized water, 4.35g (water content 50%, 30mmol) MNNG is taken to be suspended in 20mL methanol and be slowly added dropwise in reaction solution
In, it is warming up to 80 DEG C of back flow reaction 2h.50 DEG C are cooled to hereinafter, being slowly added to KOH aqueous solution (KOH/H2O=2.8g/15mL),
It is warming up to 80 DEG C of back flow reaction 3h again；It is cooled to room temperature, with dilute HNO3Adjusting pH is 3-4, and cool overnight, it is heavy that suction filtration obtains yellow
It forms sediment, is washed 2 times with dehydrated alcohol, be dried to obtain yellow solid, purity is greater than 99%, i.e. 3- amino -3'- nitramino -5,5'-
Connection -1,2,4- triazole (yield 74%).
In the present embodiment, the total recovery that 3- amino -3'- nitramino -5,5'- joins -1,2,4- triazoles is about 49%.
The infrared spectrum of 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole, TG-DSC curve are respectively such as Fig. 1 and figure
Shown in 2, the skeletal vibration that triazole ring can be found in Fig. 1 is 1400~1500cm-1,820cm-1 or so, is bent the vibration of NH2
Dynamic absorption peak is near 3000~3400cm-1,2500cm-1；In addition, occurring NO2 absorption peak at 1318, it is possible thereby to prove
The substance 3 finally obtained is containing triazole ring skeleton, NO2 and (in 1200~1800cm-1 appearance, and this figure does not have there is no C=O
There is the strong peak in this region)；The chemical combination has good thermal stability as can be seen from Figure 2: exothermic peak there are two on the curve,
Thermally decomposing peak temperature is respectively 225 DEG C and 297 DEG C, and first exothermic peak peak shape is wider, and span is larger, illustrates the compound at this time
Experiencing the process that slowly decomposition, thermal discharge are small；3- amino -3'- nitramino -5,5'- connection-it can be seen from TG-DSC curve
The decomposition starting temperature of 1,2,4- triazole be 160 DEG C, weightless process only one, illustrate compound experience two thermally decomposed
Journey be it is continuous continual, the transformation of intermediate not crystal phase, whole process weight-loss ratio is 36.26%.
The 13C NMR test data of 1 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole of table
The MS test data of 2 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole of table
Schemed by the 13C NMR of table 1 it is known that 4 kinds of environment C of the compound, respectively correspond the list at for 163.08ppm
Peak is the carbon atom peak position on C-NH2, the unimodal carbon atom peak position on C-NHNH2 at 161.89ppm, at 155.32ppm
The unimodal carbon atom peak position on C=NCNH2, the unimodal of the place 154.59ppm is carbon atom peak position on CN=CNHNH2, i.e.,
Four kinds of carbon atom peak positions that 3- amino -3'- nitramino -5,5'- joins in -1,2,4- triazole compounds are all found, and can be proved
Its structure is exactly 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole.
It becomes apparent from and finds out additionally by the Information in Mass Spectra in table 2,209.9 be 3- amino -3'- nitramino -5,5'- connection -1,
2,4- triazoles lose one [H+] and the fragment peak of generation, because of wherein 3- amino -3'- nitramino -5,5'- connection -1,2,4- tri-
The molecular weight of azoles ontology is 211.06, and the molecular weight for subtracting a Hydrogen Proton should be 210.06, this is poor with 209.9 on spectrogram
0.16, meet nominal error range, the two can be determined that the same substance.
By above series of characterization it is found that we by the method for the invention gained compound be both 3- amino -3'- nitre ammonia
Base -5,5'- connection -1,2,4- triazole.
Embodiment 2
(1) synthesis of 3- amino -1H-1,2,4- triazole -5- carboxylic acid, ethyl ester
Dehydrated alcohol 90mL is added in 250mL three-necked bottle, takes 3- amino -1H-1, -5 carboxylic acid 12.8g of 2,4- triazole
(10mmol), stirring make it be suspended in dehydrated alcohol, take 50% smoke H of 6mL2SO4It is slowly added dropwise in reaction solution, is warming up to 85 DEG C
Back flow reaction 12h, natural cooling, revolving remove part ethyl alcohol, and precipitation obtains 3- amino -1H-1,2,4- triazole -5- carboxylic acid, ethyl esters
Sulfate precipitation.20mL distilled water is added to precipitating, with NaOH (5molL-1) adjusting pH be 5-6, suction filtration obtain white precipitate,
It is washed 2-3 times with dehydrated alcohol, is dried to obtain 3- amino -1H-1,2,4- triazole -5- carboxylic acid, ethyl esters (yield 62%).
(2) synthesis of 3- amino -1H-1,2,4- triazole -5- carbohydrazide
3- amino -1H-1,2,4- triazole -5- carboxylic acid, ethyl ester 4.68g (30mmol) are added into 50mL single port bottle, slowly drip
Add 80% hydrazine hydrate 9.6mL, be stirred to react 14h at room temperature, filters and obtain white solid, dry obtained 3- amino -1H-1,2,4-
Triazole -5- carbohydrazide (yield 79%).
(3) synthesis of 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole
3- amino -1H-1,2,4- triazole -5- carbohydrazide 2.1g (14.8mmol) is added into 100mL there-necked flask and suspends
In 20mL deionized water, 4.35g (water content 50%, 30mmol) MNNG is taken to be suspended in 20mL methanol and be slowly added dropwise in reaction solution
In, it is warming up to 80 DEG C of back flow reaction 2h.50 DEG C are cooled to hereinafter, being slowly added to KOH aqueous solution (KOH/H2O=2.8g/15mL),
It is warming up to 80 DEG C of back flow reaction 3h again；It is cooled to room temperature, uses HNO3Adjusting pH is 3-4, and cool overnight, it is heavy that suction filtration obtains yellow
It forms sediment, is washed 2 times, be dried to obtain yellow solid (yield 64%) with dehydrated alcohol, purity is greater than 99%.
In the present embodiment, the total recovery that 3- amino -3'- nitramino -5,5'- joins -1,2,4- triazoles is about 31%.
Embodiment 3
(1) synthesis of 3- amino -1H-1,2,4- triazole -5- carboxylate methyl ester
Anhydrous methanol 90mL is added in 250mL three-necked bottle, takes 3- amino -1H-1, -5 carboxylic acid 12.8g of 2,4- triazole
(10mmol), stirring make it be suspended in anhydrous methanol, take 6mL 98%H2SO4It is slowly added dropwise in reaction solution, is warming up to 85 DEG C of reflux
12h, natural cooling are reacted, revolving removes part methanol, and precipitation obtains 3- amino -1H-1,2,4- triazole -5- carboxylate methyl ester sulfuric acid
Salt precipitating.20mL distilled water is added to precipitating, with NaOH (5molL-1) adjusting pH be 5-6, suction filtration obtain white precipitate, with nothing
Water-ethanol washs 2-3 times, is dried to obtain 3- amino -1H-1,2,4- triazole -5- carboxylate methyl esters (yield 72%).
(2) synthesis of 3- amino -1H-1,2,4- triazole -5- carbohydrazide
3- amino -1H-1,2,4- triazole -5- carboxylate methyl ester 4.26g (30mmol) are added into 50mL single port bottle, slowly drip
Add 80% hydrazine hydrate 9.6mL, be stirred to react 14h at room temperature, filters and obtain white solid, dry obtained 3- amino -1H-1,2,4-
Triazole -5- carbohydrazide (yield 90%).
(3) synthesis of 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole
3- amino -1H-1,2,4- triazole -5- carbohydrazide 2.1g (14.8mmol) is added into 100mL there-necked flask and suspends
In 20mL deionized water, 4.35g (water content 50%, 30mmol) MNNG is taken to be suspended in 20mL methanol and be slowly added dropwise in reaction solution
In, it is warming up to 80 DEG C of back flow reaction 2h.50 DEG C are cooled to hereinafter, being slowly added to KOH aqueous solution (KOH/H2O=2.8g/15mL),
It is warming up to 80 DEG C of back flow reaction 3h again；It is cooled to room temperature, adjusting pH with dilute HCl is 3-4, and cool overnight, it is heavy that suction filtration obtains yellow
It forms sediment, is washed 2 times, be dried to obtain yellow solid (yield 65%) with anhydrous methanol, purity is greater than 99%.
In the present embodiment, the total recovery that 3- amino -3'- nitramino -5,5'- joins -1,2,4- triazoles is about 42%.
Embodiment 4
(1) synthesis of 3- amino -1H-1,2,4- triazole -5- carboxylic acid, ethyl ester
Dehydrated alcohol 100mL is added in 250mL three-necked bottle, takes 3- amino -1H-1, -5 carboxylic acid 15.36g of 2,4- triazole
(12mmol), stirring make it be suspended in dehydrated alcohol, take 50% smoke H of 7mL2SO4It is slowly added dropwise in reaction solution, is warming up to 85 DEG C
Back flow reaction 11h, natural cooling, revolving remove part ethyl alcohol, and precipitation obtains 3- amino -1H-1,2,4- triazole -5- carboxylic acid, ethyl esters
Sulfate precipitation.20mL distilled water is added to precipitating, with NaOH (5molL-1) adjusting pH be 5-6, suction filtration obtain white precipitate,
It is washed 2-3 times with dehydrated alcohol, is dried to obtain 3- amino -1H-1,2,4- triazole -5- carboxylate methyl esters (yield 65%).
(2) synthesis of 3- amino -1H-1,2,4- triazole -5- carbohydrazide
3- amino -1H-1,2,4- triazole -5- carboxylic acid, ethyl ester 4.26g (30mmol) are added into 50mL single port bottle, slowly drip
Add 80% hydrazine hydrate 10.2mL, be stirred to react 10h at room temperature, filters and obtain white solid, dry obtained 3- amino -1H-1,2,
4- triazole -5- carbohydrazide (yield 81%).
(3) synthesis of 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole
3- amino -1H-1,2,4- triazole -5- carbohydrazide 2.2g (15.5mmol) is added into 100mL there-necked flask and suspends
In 20mL deionized water, 4.35g (water content 50%, 30mmol) MNNG is taken to be suspended in 20mL methanol and be slowly added dropwise in reaction solution
In, it is warming up to 80 DEG C of back flow reaction 2.5h.50 DEG C are cooled to hereinafter, being slowly added to KOH aqueous solution (KOH/H2O=2.8g/
15mL), 80 DEG C of back flow reaction 3.5h are warming up to then；It is cooled to room temperature, with dilute HNO3Adjusting pH is 3-4, and cool overnight filters
It to yellow mercury oxide, is washed 2 times with dehydrated alcohol, is dried to obtain yellow solid, i.e. 3- amino -3'- nitramino -5,5'- connection -1,2,
4- triazole (yield 64%), purity are greater than 99%.
In the present embodiment, the total recovery that 3- amino -3'- nitramino -5,5'- joins -1,2,4- triazoles is about 34%.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, however, it is to be understood that ability
Field technique personnel can be designed that a lot of other modification and implementations, these modifications and implementations will fall in the application public affairs
Within the scope and spirit opened.It more specifically, can be to the group of theme combination layout in range disclosed in the present application
A variety of variations and modifications are carried out at component and/or layout.In addition to variations and improvements to the component parts and or layout,
To those skilled in the art, other purposes also will be apparent.
Claims (10)
1. a kind of richness nitrogen energetic material 3- amino -3'- nitramino -5,5'- joins -1,2,4- triazoles, it is characterised in that its structure
Formula is as follows:
2. the preparation of richness nitrogen energetic material 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole as described in claim 1
Method, it is characterised in that the following steps are included:
(1) synthesis of 3- amino -1H-1,2,4- triazole -5- carboxylate methyl ester
Anhydrous alcohols solvent and 3- amino -1H-1, -5 carboxylic acid of 2,4- triazole are taken, stirring makes 3- amino -1H-1,2,4- tri- nitrogen
- 5 carboxylic acid of azoles, which is suspended in anhydrous alcohols solvent, obtains reaction solution, and concentrated sulfuric acid catalyst is slowly added dropwise in reaction solution, heating
Flow back at least 2h, then natural cooling, and revolving removes partial solvent, and precipitation obtains 3- amino -1H-1,2,4- triazole -5- carboxylic acids
Ester sulfate precipitation；Distilled water is added to the precipitating, adjusting pH is 5-6, and suction filtration obtains white precipitate, washed with dehydrated alcohol
It washs, is dried to obtain 3- amino -1H-1,2,4- triazole -5- carboxylates；
(2) synthesis of 3- amino -1H-1,2,4- triazole -5- carbohydrazide
3- amino -1H-1 is taken, the hydrazine hydrate that hydrazine mass content is 80%, room temperature is slowly added dropwise to it in 2,4- triazole -5- carboxylates
Under be stirred to react overnight, suction filtration obtains white solid, dry obtained 3- amino -1H-1,2,4- triazole -5- carbohydrazides；
(3) synthesis of 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole
3- amino -1H-1 is taken, 2,4- triazole -5- carbohydrazides are simultaneously suspended in deionized water, take a certain amount of N- methyl N-nitro-N sub-
Nitroguanidine is suspended in solvent, and the latter is slowly dropped in the former and obtains reaction solution, is warming up to back flow reaction, after the reaction was completed
50 DEG C are cooled to hereinafter, be then slowly added into KOH solution, then be warming up to back flow reaction, is cooled to room temperature after the reaction was completed, use is dilute
Acid for adjusting pH is 3-4, and cool overnight filters and obtains yellow mercury oxide, washed with dehydrated alcohol, be dried to obtain yellow solid product 3-
Amino -3'- nitramino -5,5'- connection -1,2,4- triazole.
3. the system of richness nitrogen energetic material 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole according to claim 2
Preparation Method, it is characterised in that step (1) the anhydrous alcohols solvent and 3- amino -1H-1, the use of -5 carboxylic acid of 2,4- triazole
Ratio is -5 carboxylic acid of suspension 0.08-0.15mol3- amino -1H-1,2,4- triazole in the anhydrous alcohols solvent of every 1L.
4. richness nitrogen energetic material 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole according to claim 2 or 3
Preparation method, it is characterised in that the anhydrous alcohols solvent is anhydrous methanol or dehydrated alcohol.
5. the system of richness nitrogen energetic material 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole according to claim 2
Preparation Method, it is characterised in that step (1) described concentrated sulfuric acid catalyst is that mass fraction is 50% smoke H2SO4 or 98% dense sulphur
Acid, anhydrous alcohols solvent described in every 1L is corresponding to use 0.065-0.075L concentrated sulfuric acid catalyst.
6. the system of richness nitrogen energetic material 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole according to claim 2
Preparation Method, it is characterised in that the use ratio of step (2) 3- amino -1H-1,2,4- triazole -5- carboxylates and 80% hydrazine hydrate
Example is that every 1mol3- amino -1H-1,2,4- triazole -5- carboxylate uses 80% hydrazine hydrate of 0.3-0.35L.
7. the rich nitrogen energetic material 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole according to claim 2 or 6
Preparation method, it is characterised in that the 3- amino -1H-1,2,4- triazole -5- carboxylates are 3- amino -1H-1,2,4- triazole -5-
The mixture of any one or two kinds in carboxylate methyl ester and 3- amino -1H-1,2,4- triazole -5- carboxylic acid, ethyl ester.
8. the system of richness nitrogen energetic material 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole according to claim 2
Preparation Method, it is characterised in that step (3) 3- amino -1H-1,2,4- triazole -5- carbohydrazides and the N- methyl N-nitro -
The molar ratio of N nitrosoguanidine is 4.9-5.2:1；The concentration of the KOH solution is 0.18-0.20g/mL, every to use 1molN- first
Base-N- nitro-N nitrosoguanidine then uses KOH solution described in 0.5L.
9. the system of richness nitrogen energetic material 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole according to claim 2
Preparation Method, it is characterised in that in step (1), the time of back flow reaction is 10-14h；In step (3), first time back flow reaction
Time is 1-3h, and the time of second of back flow reaction is 2-4h.
10. the system of richness nitrogen energetic material 3- amino -3'- nitramino -5,5'- connection -1,2,4- triazole according to claim 2
Preparation Method, it is characterised in that step (3) diluted acid is dust technology or dilute sulfuric acid；Suspension N- methyl N-nitro-N nitroso
The solvent of guanidine is methanol or ethyl alcohol.
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