CN105777575B - The method for synthesizing tetranitro amine tetrasodium salt - Google Patents

The method for synthesizing tetranitro amine tetrasodium salt Download PDF

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CN105777575B
CN105777575B CN201410825890.XA CN201410825890A CN105777575B CN 105777575 B CN105777575 B CN 105777575B CN 201410825890 A CN201410825890 A CN 201410825890A CN 105777575 B CN105777575 B CN 105777575B
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tetranitro
glycoluril
temperature
reaction
tetrasodium salt
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CN105777575A (en
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哈恒欣
朱朝阳
张博斌
黄浩南
孙忠祥
王素芳
王宏志
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Hubei Institute of Aerospace Chemical Technology
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Abstract

A kind of method for synthesizing tetranitro amine tetrasodium salt, using glycoluril as raw material, the step of neutralization reaction three of the nitration reaction through glycoluril, the hydrolysis of tetranitro glycoluril and tetranitro amine ethane prepares tetranitro amine tetrasodium salt.This method safety simple to operate, the kind and usage amount of solvent during reduction, three-step reaction obtain the gross production rate height of tetranitro amine tetrasodium salt, technique favorable reproducibility.

Description

The method for synthesizing tetranitro amine tetrasodium salt
Technical field
The present invention relates to the synthetic technology of high yield synthesis tetranitro amine tetrasodium salt.The tetranitro amine four that this method synthesizes Sodium salt has preferable heat endurance and higher explosion velocity, can have dechlorination work(as high explosive, propellant and pyrotechnic composition The high energy component of energy.
Background technology
Tetranitro amine tetrasodium salt（Abridge Na4TNAE) it is a kind of promising new high density, high-power and stable fried Medicine.Theoretical calculation detonation parameter is 42.7GPa, explosion velocity 10.9km/s, and detonation energy reaches 7081kJ/mol, is known to contain energy One of energy highest compound in material.Because it has positive oxygen balance and gratifying machine security performance, thus High energy oxidizer can be used as to be used in advanced solid rocket propellant.
The standard molar combustion enthalpy of tetranitro amine tetrasodium salt is -2090kJ/mol, and mark is calculated using Hess law in 298K An accurate mole enthalpy of formation is+190kJ/mol（Assuming that combustion product：CO2；H2O；N2；Na2O）, it is as other high nitrogen compounds Endothermic compound, impact sensitivity and heat endurance are similar to nitramine.It is a kind of high energy oxygen but the compound has positive oxygen balance Agent, its decomposition temperature are lower than AP（192℃）, to realizing that propellant Low vulnerability is favourable.Particularly the compound to friction compared with Insensitiveness, this point are undoubtedly critically important to composite solidpropellant.
From the point of view of demand analysis, 4 sodium atoms are contained in the compound, are particularly suitable for large-sized solid boost motor HTPB propulsions It is used to eliminate the hydrogen chloride in combustion gas in agent.It is to use KNO that the optimal path proposed in Demonstration Report is integrated according to big boosting3Come Hydrogen chloride is neutralized, but the approach significantly reduces propellant specific impulse.Theoretical calculation shows, to three constituent elements of 87% solids content HTPB propellants, its theoretical specific impulse are 264s.As the KNO for adding 30%3When, can be with the hydrogen chloride in neutralized reaction product, but promote Agent theoretical specific impulse is reduced to 244s, decreases by 20s, and energy loss is quite big, has nearly reached down state.And with 31% Na4TNAE substitutes AP, hydride hydrogen can not only be completely eliminated, and theoretical specific impulse can reach 262s, almost not reduce.Such as Fruit does not have to sodium salt but uses lithium salts instead, and theoretical specific impulse even can keep the level suitable with tripropellant.Therefore, if 15% or so Na is only added in propellant formulation4TNAE partially removes hydrogen chloride, and not only energy will not reduce, and can be with , it is expected that big influence is there will not be to propellant other performance.
《War industry's journal》Described in 3rd interim " study on the synthesis of tetranitro glycoluril and its hydrolysate " one texts in 1980 Synthesize tetranitro glycoluril（Abridge TENGU）, tetranitro amine ethane（Abridge TNAE）And the method for tenitramine tetrasodium salt, but by text The low yield for the tetranitro amine tetrasodium salt that the post-processing approach of middle introduction obtains, only 36.04% or so.
In a word, the shortcomings of the prior art is that three step gross production rates of synthesis tetranitro amine tetrasodium salt technology are low, is reacted In journey and last handling process, and dosage wide in variety using solvent is big.
The content of the invention
A kind of synthesis tetranitro amine tetrasodium salt is provided it is an object of the invention to overcome the above-mentioned deficiency of prior art Method, this method safety simple to operate, the kind and usage amount of solvent during reduction, three-step reaction obtain the sodium of tetranitro amine four The gross production rate of salt is high, technique favorable reproducibility.
The tetranitro amine tetrasodium salt of the present invention is the hydrate of tetranitro amine tetrasodium salt two with two crystallizations water （Na4TNAE·2H2O）, specific synthetic route is as follows：
;
The present invention technical solution be：With glycoluril (Glycoluril) for raw material, the nitration reaction through glycoluril, four Nitro glycoluril（TENGU）Hydrolysis and tetranitro amine ethane（TNAE）The step of neutralization reaction three prepare the sodium of tetranitro amine four Salt.
The nitration reaction of glycoluril of the present invention, comprises the following steps：（1）Fuming nitric aicd is added in reaction vessel, will When temperature is down to 10 DEG C, glycoluril is added, after glycoluril dissolving, obtains glycoluril-fuming nitric aicd solution；（2）Glycoluril-fuming nitric aicd is molten The temperature of liquid is down to 0~5 DEG C, and acetic anhydride is added dropwise, and dropping temperature is maintained at 0~5 DEG C；（3）Acetic anhydride is finished, and nitrification temperature is kept After 0~5 DEG C, nitration reaction 4h, rise nitrification temperature continues 2~3h of nitrification to 5~10 DEG C；Nitration reaction starts 10min bottles Inside there is precipitation to produce, nitrification thermograde progressively heats up；（4）After nitration reaction, by step（3）Material be down to -10 DEG C~0 DEG C, material filtering in reaction bulb, white solid tetranitro glycoluril is obtained, white solid tetranitro glycoluril is washed with dichloromethane To neutrality, it is immersed in stand-by in dichloromethane.
In the nitration reaction of the glycoluril, mass ratio=1 that feeds intake of glycoluril and fuming nitric aicd：10~1：50, acetic anhydride with Volume ratio=1 of fuming nitric aicd：2.
The step of nitration reaction of the glycoluril（3）In, nitrification thermograde progressively heats up, i.e.,：5 DEG C are used as gradient, Heated up again 5 DEG C after being kept for 2 hours, that is, start nitrification temperature and be maintained at 0 DEG C, nitration reaction 2h, raise 5 DEG C, that is, nitrify temperature liter To 5 DEG C, continue to nitrify 2h, then raise 5 DEG C, that is, nitrify temperature and rise to 10 DEG C, then kept for 2~3 hours.
The hydrolysis of tetranitro glycoluril of the present invention, comprises the following steps：（1）Sodium hydroxide is dissolved in distilled water In obtain sodium hydrate aqueous solution, sodium hydrate aqueous solution temperature is down to 0~5 DEG C；（2）Four in dichloromethane will be immersed in Nitro glycoluril filters, press dry after add in the sodium hydrate aqueous solution of stirring and hydrolyze, 10 DEG C of hydrolysis temperature ﹤；Tetranitro glycoluril with The ratio between sodium hydroxide mole is：1：10~1：5；（3）After tetranitro glycoluril finishes, hydrolysis 0.5h is kept；（4）It is slowly added to dense sulphur Sour neutralization procedure（3）Reaction solution to highly acid, 5 DEG C of neutral temperature ﹤；（5）Filtered after adding absolute ether stirring extraction, with nothing White crystal sodium sulphate in water washed with ether sand core funnel, filtrate layered, upper strata ether extraction liquid is done with anhydrous sodium sulfate Dry more than 4h；（6）To step（5）In ether extraction liquid carry out normal temperature vacuum distillation, ether is evaporated off, to a large amount of solids separate out, The dichloromethane of 2-3 times of volume is added, is filtrated to get white solid tetranitro amine ethane；（7）Tetranitro amine ethane is dissolved in Equipped with absolute methanol container, stirring stands liquid separation, except sub-cloud impurity, supernatant liquor is fitted into stand-by in container to after dissolving.
In the hydrolysis of tetranitro glycoluril of the present invention, the molar concentration 3.0mol/L- of sodium hydrate aqueous solution Mol ratio=1 of 4.0mol/L, sodium hydroxide and the concentrated sulfuric acid：1-1：2.
In the hydrolysis of tetranitro glycoluril of the present invention, the method that pH-value is tested using pH test paper is hydrolyzed to control Journey, sodium hydrate aqueous solution pH value=14, finish pH=7-10 of material after tetranitro glycoluril, the concentrated sulfuric acid is added dropwise finish after material pH =1。
The step of hydrolysis of tetranitro glycoluril of the present invention（5）And step（6）Between also include:By filtrate layered The absolute ether extracting and demixing again of lower aqueous layer afterwards, step is incorporated to by upper strata ether layer（5）Ether extraction liquid in.
The neutralization reaction of tetranitro amine ethane of the present invention comprises the following steps：（1）The reaction for being placed on ice-water bath is held The absolute methanol liquid of tetranitro amine ethane is added in device, treats that temperature is down to 0 DEG C；（2）Sodium hydroxide is dissolved in into absolute methanol to obtain To the methanol solution of sodium hydroxide, the methanol solution of sodium hydroxide is slowly added dropwise to reaction bulb；（3）1- is stirred after finishing 4h, filter, vacuum decompression drying under normal temperature, obtain white solid tetranitro amine tetrasodium salt.
In the neutralization reaction of the tetranitro amine ethane；The molar concentration 0.01mol/L- of sodium hydroxide and absolute methanol 1.5mol/L.Tetranitro amine ethane is highly soluble in absolute methanol in the neutralization reaction of the tetranitro amine ethane, can use up during dissolving Amount reduces the dosage of absolute methanol.White tetranitro amine ethane is dissolved in absolute methanol, is stored in the list for being stamped glass stopper In mouth flask, its hydrolysis in room temperature humid air is reduced, reduces loss of product.
The mol ratio of the neutralization reaction of the tetranitro amine ethane, tetranitro amine ethane and sodium hydroxide is 1：4.00~1： 4.01。
The present invention has the beneficial effect that compared with prior art：
（1）Present invention uses the nitrification system different from patent US4487938, and the nitrification system is in experimentation It is safe, and experimental implementation is simple.
（2）Building-up process dropping temperature of the present invention is relatively low, and when avoiding being added dropwise acetic anhydride, heat release is violent, makes course of reaction temperature Spend easily controllable, safe operation is reliable.
（3）Temperature is nitrified in building-up process of the present invention progressively to heat up using gradient, because when nitration reaction just starts, reaction Acutely, heat release is obvious, and low temperature nitrification makes course of reaction easily controllable, safe and reliable, and nitrification temperature is stepped up after reacting balance, Be advantageous to improve the nitrification conversion ratio of glycoluril, improve the yield of tetranitro glycoluril.
（4）In building-up process of the present invention, reaction temperature is down to -10 DEG C~0 DEG C before discharging, is to reduce tetranitro glycoluril Solubility in fuming nitric aicd, improve the yield of tetranitro glycoluril.
（5）Neutrality only is washed till with dichloromethane during after-treatment products of the present invention, is avoided using frozen water dissolving part tetranitro Glycoluril, tetranitro glycoluril yield can be improved.Because tetranitro glycoluril has preferable heat endurance, but its water stability is poor, 40 When DEG C relative humidity is 90~95%, it is changed into liquid after 3~4 days, last handling process avoids contact with water, and when being washed till neutrality, uses Dichloromethane soaks, and avoids contact with the steam in air, can reduce the loss of tetranitro glycoluril, improves the nitre of final goal product four The yield of base amine tetrasodium salt.
（6）Present invention post processing uses single solvent dichloromethane, avoids using mixed solvent, pacifies last handling process Entirely, it is easy to operate, it is recyclable.
（7）Hydrolytic process is controlled using the method for PH test paper test pH-value, make that hydrolysis carries out complete and can Strong acid dosage is controlled, improves the yield of tetranitro amine ethane.
（8）Ether twice is carried out to the reaction solution containing product to extract, and can be improved the ether extraction effect of reaction solution, be improved The yield of tetranitro amine ethane.
（9）White tetranitro amine ethane is dissolved in absolute methanol, is stored in the single-necked flask for being stamped glass stopper, is reduced Its hydrolysis in room temperature humid air, the loss of tetranitro amine ethane is reduced, improve the sodium of final goal product tetranitro amine four The yield of salt.
（10）With article " Synthesis and Properties of Tetrasodium Salt of 1,1,2,2- Tetranitroaminoethane " tetranitro amine tetrasodium salt building-up process is compared, and N-process is carried out in ice-water bath, can Avoid neutralization reaction heat release violent, make course of reaction safely controllable.
（11）Synthesis and the last handling process of tetranitro amine tetrasodium salt are carried out by the present invention, final product can be effectively improved Na4TNAE·2H2O yield is to more than 80%.
Embodiment
With reference to embodiment, the present invention is described in detail.
Embodiment 1:
The preparation of tetranitro glycoluril：It is being equipped with the 3000ml of reflux condenser, thermometer, agitator, constant pressure funnel In four mouthfuls of round-bottom reaction flasks, 500ml fuming nitric aicds are added.When the temperature to about 10 DEG C, 20g glycolurils are rapidly joined, are stirred to molten Solution, obtains glycoluril-fuming nitric aicd solution；The temperature of glycoluril-fuming nitric aicd solution is down to 0~5 DEG C, 250ml acetic anhydrides are added dropwise, Dropping temperature is maintained at 0~5 DEG C；Acetic anhydride finishes, and nitrification temperature is maintained at 0~5 DEG C, after nitration reaction 4h, rise nitrification temperature Degree continues to nitrify 3h to 5~10 DEG C；Nitrification thermograde progressively heats up, 5 DEG C are used as gradient, and holding heats up 5 again after 2 hours DEG C, that is, start nitrification temperature and be maintained at 0 DEG C, nitration reaction 2h, raise 5 DEG C, that is, nitrify temperature and rise to 5 DEG C, continue to nitrify 2h, then 5 DEG C of rise, that is, nitrify temperature and rise to 10 DEG C, then kept for 3 hours.
Nitration reaction starts have precipitation to produce in 10min bottles, and nitrification thermograde progressively heats up, and precipitation capacity is with reaction temperature Degree, reaction time are continuously increased, and when precipitating complete, the mixture in reaction bulb is down into -10 DEG C~0 DEG C, stops reacting, in bottle Mixture filters through sand core funnel, and white solid tetranitro glycoluril is washed till neutrality with a large amount of dichloromethane, is immersed in dichloromethane In it is stand-by.
The preparation of tetranitro amine ethane：It is being equipped with tetra- mouthfuls of the 3000ml of reflux condenser, thermometer, glass stopper, agitator In reaction bulb, 28gNaOH and 200ml distilled water is added, solution temperature in bottle is down to 0~5 by stirring to dissolving with ice-water bath ℃；The neutral tetranitro glycoluril being immersed in dichloromethane is filtered in sand core funnel after pressing dry, slowly add reaction bulb In, keep 10 DEG C of hydrolysis temperature ﹤；After tetranitro glycoluril finishes, it is 8 to test solution pH value with PH test paper, continues stirring and keeps water 0.5h is solved, then concentrated sulfuric acid neutralization reaction liquid is slowly added dropwise with constant pressure funnel to make it to highly acid, pH value 1, neutral temperature ﹤ 5℃；The concentrated sulfuric acid, which is added dropwise, to be finished, and adds the stirring extraction of 500ml absolute ethers, stops stirring, and sand core funnel filtering is anhydrous with 250ml White crystal sodium sulphate in washed with ether funnel, filtrate is layered with separatory funnel, upper strata ether extraction liquid is loaded into single port circle In the flask of bottom, secondary clearing again after lower floor's liquid is extracted with 250ml absolute ethers, by ether extraction liquid anhydrous sodium sulfate drying 4h More than；Ether is removed under reduced pressure with Rotary Evaporators normal temperature, is separated out to a large amount of solids, is added the dichloromethane of 2~3 times of volumes, is stirred White solid tetranitro amine ethane is filtrated to get after mixing.The single port that tetranitro amine ethane is dissolved in 250m absolute methanols in time burns In bottle, stirring is poured into and liquid separation is stood in separatory funnel, except sub-cloud impurity, supernatant liquor is fitted into single-necked flask to after dissolving It is stand-by to cover glass stopper, obtains tetranitro amine ethane-methanol solution.
The preparation of tetranitro amine tetrasodium salt：In 2000ml single necked round bottom flask, it is anhydrous to add 17.5gNaOH and 1750ml Methanol is stirred to dissolving, obtains sodium hydroxide-methanol solution；Toward the outfit reflux condenser, thermometer, constant pressure for being placed in ice-water bath Dropping funel, agitator tetra- mouthfuls of reaction bulbs of 3000ml in, add tetranitro amine ethane-absolute methanol solution, treat that temperature is down to 0 ~5 DEG C, it is slowly added dropwise sodium hydroxide-the methanol solution prepared into reaction bulb, is added dropwise after finishing and stirs 1~4h, filtering, with nothing Water methanol rinses, and is filtered dry rear normal-temperature vacuum and is dried under reduced pressure, obtains white solid powder Na4TNAE·2H2The g of O 46.7, yield 84.16% （Theoretical yield 55.49g）.
Embodiment 2:
The preparation of tetranitro glycoluril：It is being equipped with the 3000ml of reflux condenser, thermometer, agitator, constant pressure funnel In four mouthfuls of round-bottom reaction flasks, 600ml fuming nitric aicds are added.When the temperature to about 10 DEG C, 30g glycolurils are rapidly joined, are stirred to molten Solution, obtains glycoluril-fuming nitric aicd solution；The temperature of glycoluril-fuming nitric aicd solution is down to 0~5 DEG C, 300ml acetic anhydrides are added dropwise, Dropping temperature is maintained at 0~5 DEG C；Acetic anhydride finishes, and nitrification temperature is maintained at 0~5 DEG C, after nitration reaction 4h, rise nitrification temperature Degree continues to nitrify 3h to 5~10 DEG C；Nitrification thermograde progressively heats up, 5 DEG C are used as gradient, and holding heats up 5 again after 2 hours DEG C, that is, start nitrification temperature and be maintained at 0 DEG C, nitration reaction 2h, raise 5 DEG C, that is, nitrify temperature and rise to 5 DEG C, continue to nitrify 2h, then 5 DEG C of rise, that is, nitrify temperature and rise to 10 DEG C, then kept for 3 hours.
Nitration reaction starts have precipitation to produce in 10min bottles, and nitrification thermograde progressively heats up, and precipitation capacity is with reaction temperature Degree, reaction time are continuously increased, and when precipitating complete, the mixture in reaction bulb is down into -10 DEG C~0 DEG C, stops reacting, in bottle Mixture filters through sand core funnel, and white solid tetranitro glycoluril is washed till neutrality with a large amount of dichloromethane, is immersed in dichloromethane In it is stand-by.
The preparation of tetranitro amine ethane：It is being equipped with tetra- mouthfuls of the 3000ml of reflux condenser, thermometer, glass stopper, agitator In reaction bulb, 40gNaOH and 300ml distilled water is added, solution temperature in bottle is down to 0~5 by stirring to dissolving with ice-water bath ℃；The neutral tetranitro glycoluril being immersed in dichloromethane is filtered in sand core funnel after pressing dry, slowly add reaction bulb In, keep 10 DEG C of hydrolysis temperature ﹤；After tetranitro glycoluril finishes, it is 8 to test solution pH value with PH test paper, continues stirring and keeps water 0.5h is solved, then concentrated sulfuric acid neutralization reaction liquid is slowly added dropwise with constant pressure funnel to make it to highly acid, pH value 1, neutral temperature ﹤ 5℃；The concentrated sulfuric acid, which is added dropwise, to be finished, and adds the stirring extraction of 1250ml absolute ethers, stops stirring, and sand core funnel filtering is anhydrous with 250ml White crystal sodium sulphate in washed with ether funnel, filtrate is layered with separatory funnel, upper strata ether extraction liquid is loaded into single port circle In the flask of bottom, secondary clearing again after lower floor's liquid is extracted with 250ml absolute ethers, by ether extraction liquid anhydrous sodium sulfate drying 4h More than；Ether is removed under reduced pressure with Rotary Evaporators normal temperature, is separated out to a large amount of solids, is added the dichloromethane of 2~3 times of volumes, is stirred White solid tetranitro amine ethane is filtrated to get after mixing.The single port that tetranitro amine ethane is dissolved in 250m absolute methanols in time burns In bottle, stirring is poured into and liquid separation is stood in separatory funnel, except sub-cloud impurity, supernatant liquor is fitted into single-necked flask to after dissolving It is stand-by to cover glass stopper, obtains tetranitro amine ethane-methanol solution.
The preparation of tetranitro amine tetrasodium salt：In 2000ml single necked round bottom flask, 26gNaOH and 1750ml is added without water beetle Alcohol is stirred to dissolving, obtains sodium hydroxide-methanol solution；Toward outfit reflux condenser, thermometer, the constant pressure drop for being placed in ice-water bath Liquid funnel, agitator tetra- mouthfuls of reaction bulbs of 3000ml in, add tetranitro amine ethane-absolute methanol solution, treat temperature be down to 0~ 5 DEG C, it is slowly added dropwise sodium hydroxide-the methanol solution prepared into reaction bulb, is added dropwise after finishing and stirs 1~4h, filtering, with anhydrous Methanol rinses, and is filtered dry rear normal-temperature vacuum and is dried under reduced pressure, obtains white solid powder Na4TNAE·2H2The g of O 66.90, yield 80.67% （Theoretical yield 82.93g）.
Na4TNAE·2H2O density 2.006g/cm3；200 DEG C of initial decomposition temperature, decompose 258 DEG C of peak temperature； Na4C2N8H2O8·2H2O Elemental Analysis theories（%）：C 6.09, H 1.52, N 28.43；Measured value（%）：C 6.38, H 1.06, N 28.71；Na4TNAE2H2O infrared analysis（KBr tablettings）：Characteristic peak N-NO2：1400,1395,1375,1385, 1305,1275cm-1(s), C-H：2950,2920cm-1(w)；H2O:3400 (s), 1600cm-1(w) it is and reported in the literature basic Unanimously；Nmr analysis（Acetone, internal standard HMDS）, hydrogen spectrum peak 5.84ppm, carbon spectrum peak 74.61ppm.

Claims (7)

  1. A kind of 1. method for synthesizing tetranitro amine tetrasodium salt, it is characterised in that：Using glycoluril as raw material, the nitrification through glycoluril is anti- Should, the step of neutralization reaction three of the hydrolysis of tetranitro glycoluril and tetranitro amine ethane prepare tetranitro amine tetrasodium salt；
    The nitration reaction of the glycoluril, comprises the following steps：
    （1）Fuming nitric aicd is added in reaction vessel, when cooling the temperature to 10 DEG C, glycoluril is added, after glycoluril dissolving, obtains sweet Urea-fuming nitric aicd solution；
    （2）The temperature of glycoluril-fuming nitric aicd solution is down to 0~5 DEG C, acetic anhydride is added dropwise, dropping temperature is maintained at 0~5 DEG C；
    （3）Acetic anhydride finishes, and nitrification temperature is maintained at 0~5 DEG C, after nitration reaction 4h, rise nitrification temperature to 5~10 DEG C, after 2~3h of continuous nitrification；Nitration reaction starts have precipitation to produce in 10min bottles, and nitrification thermograde progressively heats up；
    （4）After nitration reaction, by step（3）Material be down to -10 DEG C~0 DEG C, material filtering in reaction bulb, it is solid to obtain white Body tetranitro glycoluril, white solid tetranitro glycoluril is washed till neutrality with dichloromethane, is immersed in stand-by in dichloromethane；
    The hydrolysis of the tetranitro glycoluril, comprises the following steps：
    （1）Sodium hydroxide is dissolved in distilled water and obtains sodium hydrate aqueous solution, sodium hydrate aqueous solution temperature is down to 0~ 5℃；
    （2）The sodium hydrate aqueous solution reclaimed water of stirring is added after the tetranitro glycoluril being immersed in dichloromethane is filtered, pressed dry Solution, 10 DEG C of hydrolysis temperature ﹤；The ratio between tetranitro glycoluril and sodium hydroxide mole are：1：20~1：5；
    （3）After tetranitro glycoluril finishes, hydrolysis 0.5h is kept；
    （4）It is slowly added to concentrated sulfuric acid neutralization procedure（3）Reaction solution to highly acid, 5 DEG C of neutral temperature ﹤；
    （5）Filtered after adding absolute ether stirring extraction, white crystal sodium sulphate in sand core funnel is rinsed with absolute ether, filter Liquid is layered, by upper strata ether extraction liquid more than anhydrous sodium sulfate drying 4h；
    （6）To step（5）In ether extraction liquid carry out normal temperature vacuum distillation, ether is evaporated off, to a large amount of solids separate out, add 2- The dichloromethane of 3 times of volumes, it is filtrated to get white solid tetranitro amine ethane；
    （7）Tetranitro amine ethane is dissolved in equipped with absolute methanol container, stirring stands liquid separation, except sub-cloud to after dissolving Impurity, supernatant liquor are fitted into stand-by in container；
    The neutralization reaction of the tetranitro amine ethane comprises the following steps：
    （1）It is placed on adding the absolute methanol liquid of tetranitro amine ethane in the reaction vessel of ice-water bath, treats that temperature is down to 0 DEG C；
    （2）Sodium hydroxide is dissolved in absolute methanol and obtains the methanol solution of sodium hydroxide, the methanol solution of sodium hydroxide is delayed Slowly it is added dropwise in reaction bulb；
    （3）1-4h is stirred after finishing, vacuum decompression is dried under filtering, normal temperature, obtains white solid tetranitro amine tetrasodium salt.
  2. 2. the method for tetranitro amine tetrasodium salt is synthesized according to claim 1, it is characterised in that：The nitration reaction of the glycoluril In, mass ratio=1 that feeds intake of glycoluril and fuming nitric aicd：10~1：50, volume ratio=1 of acetic anhydride and fuming nitric aicd：2.
  3. 3. the method for tetranitro amine tetrasodium salt is synthesized according to claim 1, it is characterised in that：The nitration reaction of the glycoluril The step of（3）In, nitrification thermograde progressively heats up, i.e.,：5 DEG C are used as gradient, heats up 5 DEG C, that is, starts again after being kept for 2 hours Nitrification temperature is maintained at 0 DEG C, nitration reaction 2h, raises 5 DEG C, that is, nitrifies temperature and rise to 5 DEG C, continues to nitrify 2h, then raises 5 DEG C, That is nitrification temperature rises to 10 DEG C, then is kept for 2~3 hours.
  4. 4. the method for tetranitro amine tetrasodium salt is synthesized according to claim 1, it is characterised in that：The water of the tetranitro glycoluril In solution reaction, the molar concentration 3.0mol/L-4.0mol/L of sodium hydrate aqueous solution, the mol ratio of sodium hydroxide and the concentrated sulfuric acid= 1：1-1：2.
  5. 5. the method for tetranitro amine tetrasodium salt is synthesized according to claim 1, it is characterised in that：The hydrolysis of tetranitro glycoluril is anti- Ying Zhong, hydrolytic process is controlled using the method for pH test paper test pH-value, sodium hydrate aqueous solution pH value=14, finishes four nitre PH=1 for finishing rear material is added dropwise in pH=7-10 of material after base glycoluril, the concentrated sulfuric acid.
  6. 6. the method for tetranitro amine tetrasodium salt is synthesized according to claim 1, it is characterised in that：Step（5）And step（6）It Between also include:By the absolute ether extracting and demixing again of the lower aqueous layer after filtrate layered, upper strata ether layer is incorporated to step（5）'s In ether extraction liquid.
  7. 7. the method for tetranitro amine tetrasodium salt is synthesized according to claim 1, it is characterised in that：The tetranitro amine ethane In neutralization reaction；The molar concentration 0.01mol/L-1.5mol/L of sodium hydroxide and absolute methanol；Tetranitro amine ethane and hydrogen-oxygen The mol ratio for changing sodium is 1：4.00~1：8.00.
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