CN105777575A - Method used for synthesizing Na4TNAE - Google Patents
Method used for synthesizing Na4TNAE Download PDFInfo
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- CN105777575A CN105777575A CN201410825890.XA CN201410825890A CN105777575A CN 105777575 A CN105777575 A CN 105777575A CN 201410825890 A CN201410825890 A CN 201410825890A CN 105777575 A CN105777575 A CN 105777575A
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Abstract
The invention discloses a method used for synthesizing Na4TNAE. According to the method, glycoluril is taken as a raw material, and Na4TNAE is prepared via three steps including nitration of glycoluril, hydrolysis of tetranitroglycoluril, and neutralization of tetranitro aminoethane. Operation of the method is simple and safe; the kinds and using amount of solvents used in the method are reduced; total yield of Na4TNAE obtained via the three steps is high; and technological reproducibility is high.
Description
Technical field
The present invention relates to the synthetic technology of high yield synthesis tetranitro amine tetrasodium salt.The tetranitro amine tetrasodium salt that the method synthesizes has good heat stability and higher explosion velocity, can as the high energy component with dechlorination function of high explosive, propellant and pyrotechnic composition.
Background technology
Tetranitro amine tetrasodium salt (abbreviation Na4TNAE) it is a kind of promising new high density, high-power and stable explosive.Theoretical Calculation detonation parameter is 42.7GPa, and explosion velocity is 10.9km/s, and detonation energy reaches 7081kJ/mol, is one of known compound the highest containing energy in energy material.Owing to it has positive oxygen balance and gratifying machine security performance, thus can as high energy oxidizer in advanced solid rocket propellant.
The standard molar combustion enthalpy of tetranitro amine tetrasodium salt is-2090kJ/mol, and using Hesslaw to calculate standard molar formation enthalpy at 298K is that+190kJ/mol(assumes combustion product: CO2；H2O；N2；Na2O), being endothermic compound as other high nitrogen compound, impact sensitivity is similar to nitramine with heat stability.But this compound has positive oxygen balance, being a kind of high energy oxidizer, its decomposition temperature lower than AP (192 DEG C), to realizing, propellant Low vulnerability is favourable.Particularly this compound is to the relatively insensitiveness that rubs, and this point is critically important to composite solidpropellant undoubtedly.
From demand analysis, containing 4 sodium atoms in this compound, it is particularly suitable in large-sized solid booster HTPB propellant the hydrogen chloride for eliminating in combustion gas.It is adopt KNO according to the optimal path proposed in the comprehensive Demonstration Report of big boosting3Neutralize hydrogen chloride, but this approach makes propellant specific impulse significantly reduce.Theoretical Calculation shows, the three constituent element HTPB propellants to 87% solids content, its theoretical specific impulse is 264s.As the KNO adding 30%3Time, it is possible to the hydrogen chloride in neutralized reaction product, but propellant theoretical specific impulse is reduced to 244s, decreases by 20s, and energy loss is quite big, has nearly reached down state.And with the Na of 31%4TNAE replaces AP, is possible not only to be completely eliminated hydride hydrogen, and theoretical specific impulse can reach 262s, almost without reduction.If without sodium salt but use lithium salts instead, theoretical specific impulse even can keep the level suitable with tripropellant.Therefore, if propellant formulation only adds about 15% Na4TNAE carrys out partially remove hydrogen chloride, and not only energy will not reduce, and it is contemplated that other performance of propellant be there will not be big impact.
" war industry's journal " describes the method for synthesis tetranitro glycoluril (abbreviation TENGU), tetranitro amine ethane (abbreviation TNAE) and tenitramine tetrasodium salt for 1980 the 3rd in interim " study on the synthesis of tetranitro glycoluril and hydrolyzate thereof " literary composition, but the productivity of tetranitro amine tetrasodium salt that the post-processing approach introduced in literary composition obtains is low, only about 36.04%.
In a word, the three step gross production rates that the deficiency that prior art exists is synthesis tetranitro amine tetrasodium salt technology are low, course of reaction and in last handling process, use that solvent is wide in variety and consumption is big.
Summary of the invention
It is an object of the invention to overcome the above-mentioned deficiency of prior art to provide a kind of method synthesizing tetranitro amine tetrasodium salt, the method safety simple to operate, in minimizing process the kind of solvent with make consumption, three-step reaction obtains that the gross production rate of tetranitro amine tetrasodium salt is high, technique favorable reproducibility.
The tetranitro amine tetrasodium salt of the present invention is the tetranitro amine tetrasodium salt two hydrate (Na with two water of crystallization4TNAE·2H2O), concrete synthetic route is as follows:
;
The technical solution of the present invention is: with glycoluril (Glycoluril) for raw material, reacts three steps through the nitration reaction of glycoluril, the hydrolysis of tetranitro glycoluril (TENGU) and the neutralization of tetranitro amine ethane (TNAE) and prepares tetranitro amine tetrasodium salt.
The nitration reaction of glycoluril of the present invention, comprises the following steps: fuming nitric aicd is added in reaction vessel by (1), when cooling the temperature to 10 DEG C, adds glycoluril, and glycoluril obtains glycoluril-fuming nitric aicd solution after dissolving；(2) temperature of glycoluril-fuming nitric aicd solution being down to 0～5 DEG C, drip acetic anhydride, dropping temperature is maintained at 0～5 DEG C；(3) acetic anhydride finishes, and nitrated temperature is maintained at 0～5 DEG C, after nitration reaction 4h, raises nitrated temperature to 5～10 DEG C, continues nitrated 2～3h；Nitration reaction starts have precipitation to produce in 10min bottle, and nitrated thermograde progressively heats up；(4) after nitration reaction, the material of step (3) is down to-10 DEG C～0 DEG C, material filtering in reaction bulb, obtains white solid tetranitro glycoluril, white solid tetranitro glycoluril dichloromethane is washed till neutrality, is immersed in dichloromethane stand-by.
In the nitration reaction of described glycoluril, the mass ratio=1:10～1:50 that feeds intake of glycoluril and fuming nitric aicd, the volume ratio=1:2 of acetic anhydride and fuming nitric aicd.
In the step (3) of the nitration reaction of described glycoluril, nitrated thermograde progressively heats up, it may be assumed that adopting 5 DEG C is gradient, heats up 5 DEG C again after keeping 2 hours, namely start nitrated temperature and be maintained at 0 DEG C, nitration reaction 2h, raises 5 DEG C, and namely nitrated temperature rises to 5 DEG C, continue nitrated 2h, raising 5 DEG C again, namely nitrated temperature rises to 10 DEG C, then keeps 2～3 hours.
The hydrolysis of tetranitro glycoluril of the present invention, comprises the following steps: sodium hydroxide is dissolved in distilled water to obtain sodium hydrate aqueous solution, sodium hydrate aqueous solution temperature is down to 0～5 DEG C by (1)；(2) by the tetranitro glycoluril sucking filtration being immersed in dichloromethane, press dry after add hydrolysis, hydrolysis temperature 10 DEG C in the sodium hydrate aqueous solution of stirring；The ratio of tetranitro glycoluril and sodium hydroxide mole is: 1:10～1:5；(3), after tetranitro glycoluril finishes, hydrolysis 0.5h is kept；(4) reactant liquor of concentrated sulphuric acid neutralization procedure (3) it is slowly added to highly acid, neutral temperature 5 DEG C；(5) add after absolute ether stirring extracts and filter, rinse white crystal sodium sulfate in sand core funnel with absolute ether, filtrate is layered, by upper strata ether extraction liquid dry more than the 4h of anhydrous sodium sulfate；(6) ether extraction liquid in step (5) is carried out room temperature decompression distillation, ether is evaporated off, precipitates out to a large amount of solids, add the dichloromethane of 2-3 times of volume, be filtrated to get white solid tetranitro amine ethane；(7) being dissolved in by tetranitro amine ethane equipped with in absolute methanol container, stirring, to dissolving, stands separatory, removes lower floor's impurity, and the supernatant loads in container stand-by.
In the hydrolysis of tetranitro glycoluril of the present invention, the molar concentration 3.0mol/L-4.0mol/L of sodium hydrate aqueous solution, the mol ratio=1:1-1:2 of sodium hydroxide and concentrated sulphuric acid.
In the hydrolysis of tetranitro glycoluril of the present invention, adopt the method for pH reagent paper test pH-value to come controlled hydrolysis process, sodium hydrate aqueous solution pH value=14, finish the pH=7-10 of material after tetranitro glycoluril, concentrated sulphuric acid dropping finish after the pH=1 of material.
Also include between step (5) and the step (6) of the hydrolysis of tetranitro glycoluril of the present invention: the lower aqueous layer absolute ether extracting and demixing again after filtrate is layered, upper strata ether layer is incorporated in the ether extraction liquid of step (5).
The neutralization reaction of tetranitro amine ethane of the present invention comprises the following steps: (1) is placed on adding in the reaction vessel of ice-water bath the absolute methanol liquid of tetranitro amine ethane, 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 slowly added dropwise to reaction bulb；(3) stirring 1-4h after finishing, under filtration, room temperature, vacuum decompression dries, and obtains white solid tetranitro amine tetrasodium salt.
In the neutralization reaction of described tetranitro amine ethane；The molar concentration 0.01mol/L-1.5mol/L of sodium hydroxide and absolute methanol.In the neutralization reaction of described tetranitro amine ethane, tetranitro amine ethane is highly soluble in absolute methanol, can reduce the consumption of absolute methanol during dissolving as far as possible.White tetranitro amine ethane is dissolved in absolute methanol, is saved in the single port flask being stamped glass stopper, reduce its hydrolysis in room temperature humid air, reduce loss of product.
The neutralization reaction of described tetranitro amine ethane, the mol ratio of tetranitro amine ethane and sodium hydroxide is 1:4.00～1:4.01.
The present invention compared with prior art has the beneficial effect that
(1) present invention uses the nitrated system different from patent US4487938, the safety in experimentation of this nitrated system is high, and experimental implementation is simple.
(2) building-up process dropping temperature of the present invention is on the low side, it is to avoid during dropping acetic anhydride, heat release is violent, makes course of reaction temperature easily controllable, operates safe and reliable.
(3) in building-up process of the present invention, nitrated temperature adopts gradient progressively to heat up, because when nitration reaction just starts, reaction is violent, heat release is obvious, low temperature is nitrated makes course of reaction easily controllable, safe and reliable, nitrated temperature is stepped up after reacting balance, be conducive to improving the nitrated conversion ratio of glycoluril, improve the productivity of tetranitro glycoluril.
(4) in building-up process of the present invention, before discharging, reaction temperature is down to-10 DEG C～0 DEG C, is to reduce tetranitro glycoluril dissolubility in fuming nitric aicd, improves the productivity of tetranitro glycoluril.
(5) only it is washed till neutrality with dichloromethane during after-treatment products of the present invention, it is to avoid use frozen water to dissolve part tetranitro glycoluril, tetranitro glycoluril productivity can be improved.Because tetranitro glycoluril has good heat stability, but its water stability is poor, when 40 DEG C of relative humiditys are 90～95%, namely becoming liquid after 3～4 days, last handling process avoids contact with water, and when being washed till neutrality, soak with dichloromethane, avoid contact with the steam in air, the loss of tetranitro glycoluril can be reduced, improve the productivity of final goal product tetranitro amine tetrasodium salt.
(6) post processing of the present invention uses single solvent dichloromethane, it is to avoid uses mixed solvent, makes last handling process safe, easy and simple to handle, recyclable.
(7) method adopting PH reagent paper test pH-value carrys out controlled hydrolysis process, make that hydrolysis carries out completely and strong acid consumption can be controlled, improve the productivity of tetranitro amine ethane.
(8) reactant liquor containing product performs twice at ether extract, the ether extraction effect of reactant liquor can be improved, improve the productivity of tetranitro amine ethane.
(9) white tetranitro amine ethane is dissolved in absolute methanol, is saved in the single port flask being stamped glass stopper, reduces its hydrolysis in room temperature humid air, reduces the loss of tetranitro amine ethane, improves the productivity of final goal product tetranitro amine tetrasodium salt.
(10) compare with the tetranitro amine tetrasodium salt building-up process of article " SynthesisandPropertiesofTetrasodiumSaltof1,1,2; 2-Tetranitroaminoethane ", N-process carries out in ice-water bath, can avoid neutralizing exothermic heat of reaction violent, make course of reaction safely controllable.
(11) carry out synthesis and the last handling process of tetranitro amine tetrasodium salt by the present invention, end product Na can be effectively improved4TNAE·2H2The productivity of O is to more than 80%.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in detail.
Embodiment 1:
The preparation of tetranitro glycoluril: in the tetra-mouthfuls of round-bottom reaction flask of 3000ml being equipped with reflux condenser, thermometer, agitator, constant pressure funnel, adds 500ml fuming nitric aicd.When the temperature to about 10 DEG C, rapidly joining 20g glycoluril, stirring, to dissolving, obtains glycoluril-fuming nitric aicd solution；The temperature of glycoluril-fuming nitric aicd solution being down to 0～5 DEG C, drips 250ml acetic anhydride, dropping temperature is maintained at 0～5 DEG C；Acetic anhydride finishes, and nitrated temperature is maintained at 0～5 DEG C, after nitration reaction 4h, raises nitrated temperature to 5～10 DEG C, continues nitrated 3h；Nitrated thermograde progressively heats up, adopting 5 DEG C is gradient, heats up 5 DEG C again after keeping 2 hours, namely start nitrated temperature and be maintained at 0 DEG C, nitration reaction 2h, raise 5 DEG C, namely nitrated temperature rises to 5 DEG C, continuing nitrated 2h, then raise 5 DEG C, namely nitrated temperature rises to 10 DEG C, then keeps 3 hours.
Nitration reaction starts have precipitation to produce in 10min bottle, nitrated thermograde progressively heats up, precipitation capacity was continuously increased with reaction temperature, response time, when precipitating complete, mixture in reaction bulb is down to-10 DEG C～0 DEG C, stopped reaction, in bottle, mixture filters through sand core funnel, white solid tetranitro glycoluril is washed till neutrality with a large amount of dichloromethane, is immersed in dichloromethane stand-by.
The preparation of tetranitro amine ethane: in the tetra-mouthfuls of reaction bulbs of 3000ml being equipped with reflux condenser, thermometer, glass stopper, agitator, adds 28gNaOH and 200ml distilled water, and solution temperature in bottle, to dissolving, is down to 0～5 DEG C with ice-water bath by stirring；The neutral tetranitro glycoluril that is immersed in dichloromethane after sucking filtration press dry in sand core funnel, is added slowly in reaction bulb, keeps hydrolysis temperature 10 DEG C；After tetranitro glycoluril finishes, be 8 with PH reagent paper test solution pH value, continue stirring keep hydrolysis 0.5h, then with constant pressure funnel be slowly added dropwise in concentrated sulphuric acid and reactant liquor make it to highly acid, pH value is 1, neutral temperature 5 DEG C；Concentrated sulphuric acid dropping is finished, add the stirring of 500ml absolute ether to extract, stop stirring, sand core funnel filters, rinse white crystal sodium sulfate in funnel with 250ml absolute ether, filtrate is layered with separatory funnel, upper strata ether extraction liquid is loaded in single necked round bottom flask, lower floor's liquid extract with 250ml absolute ether after secondary clearing again, by ether extraction liquid dry more than the 4h of anhydrous sodium sulfate；Remove ether under reduced pressure with Rotary Evaporators room temperature, precipitate out to a large amount of solids, add the dichloromethane of 2～3 times of volumes, after stirring, be filtrated to get white solid tetranitro amine ethane.Tetranitro amine ethane is dissolved in the single port flask of 250m absolute methanol in time, stirring, to dissolving, is poured standing separatory in separatory funnel into, is removed lower floor's impurity, glass stopper built by supernatant loading single port flask stand-by, obtain tetranitro amine ethane-methanol solution.
The preparation of tetranitro amine tetrasodium salt: in 2000ml single necked round bottom flask, adds the stirring of 17.5gNaOH and 1750ml absolute methanol to dissolving, obtains sodium hydroxide-methanol solution；In the tetra-mouthfuls of reaction bulbs of 3000ml being equipped with reflux condenser, thermometer, constant pressure funnel, agitator being placed in ice-water bath, add tetranitro amine ethane-absolute methanol solution, treat that temperature is down to 0～5 DEG C, sodium hydroxide-the methanol solution prepared it is slowly added dropwise in reaction bulb, dropping stirs 1～4h after finishing, filter, rinse with absolute methanol, be filtered dry rear normal-temperature vacuum drying under reduced pressure, obtain white solid powder Na4TNAE·2H2O46.7g, productivity 84.16%(theoretical yield 55.49g).
Embodiment 2:
The preparation of tetranitro glycoluril: in the tetra-mouthfuls of round-bottom reaction flask of 3000ml being equipped with reflux condenser, thermometer, agitator, constant pressure funnel, adds 600ml fuming nitric aicd.When the temperature to about 10 DEG C, rapidly joining 30g glycoluril, stirring, to dissolving, obtains glycoluril-fuming nitric aicd solution；The temperature of glycoluril-fuming nitric aicd solution being down to 0～5 DEG C, drips 300ml acetic anhydride, dropping temperature is maintained at 0～5 DEG C；Acetic anhydride finishes, and nitrated temperature is maintained at 0～5 DEG C, after nitration reaction 4h, raises nitrated temperature to 5～10 DEG C, continues nitrated 3h；Nitrated thermograde progressively heats up, adopting 5 DEG C is gradient, heats up 5 DEG C again after keeping 2 hours, namely start nitrated temperature and be maintained at 0 DEG C, nitration reaction 2h, raise 5 DEG C, namely nitrated temperature rises to 5 DEG C, continuing nitrated 2h, then raise 5 DEG C, namely nitrated temperature rises to 10 DEG C, then keeps 3 hours.
Nitration reaction starts have precipitation to produce in 10min bottle, nitrated thermograde progressively heats up, precipitation capacity was continuously increased with reaction temperature, response time, when precipitating complete, mixture in reaction bulb is down to-10 DEG C～0 DEG C, stopped reaction, in bottle, mixture filters through sand core funnel, white solid tetranitro glycoluril is washed till neutrality with a large amount of dichloromethane, is immersed in dichloromethane stand-by.
The preparation of tetranitro amine ethane: in the tetra-mouthfuls of reaction bulbs of 3000ml being equipped with reflux condenser, thermometer, glass stopper, agitator, adds 40gNaOH and 300ml distilled water, and solution temperature in bottle, to dissolving, is down to 0～5 DEG C with ice-water bath by stirring；The neutral tetranitro glycoluril that is immersed in dichloromethane after sucking filtration press dry in sand core funnel, is added slowly in reaction bulb, keeps hydrolysis temperature 10 DEG C；After tetranitro glycoluril finishes, be 8 with PH reagent paper test solution pH value, continue stirring keep hydrolysis 0.5h, then with constant pressure funnel be slowly added dropwise in concentrated sulphuric acid and reactant liquor make it to highly acid, pH value is 1, neutral temperature 5 DEG C；Concentrated sulphuric acid dropping is finished, add the stirring of 1250ml absolute ether to extract, stop stirring, sand core funnel filters, rinse white crystal sodium sulfate in funnel with 250ml absolute ether, filtrate is layered with separatory funnel, upper strata ether extraction liquid is loaded in single necked round bottom flask, lower floor's liquid extract with 250ml absolute ether after secondary clearing again, by ether extraction liquid dry more than the 4h of anhydrous sodium sulfate；Remove ether under reduced pressure with Rotary Evaporators room temperature, precipitate out to a large amount of solids, add the dichloromethane of 2～3 times of volumes, after stirring, be filtrated to get white solid tetranitro amine ethane.Tetranitro amine ethane is dissolved in the single port flask of 250m absolute methanol in time, stirring, to dissolving, is poured standing separatory in separatory funnel into, is removed lower floor's impurity, glass stopper built by supernatant loading single port flask stand-by, obtain tetranitro amine ethane-methanol solution.
The preparation of tetranitro amine tetrasodium salt: in 2000ml single necked round bottom flask, adds the stirring of 26gNaOH and 1750ml absolute methanol to dissolving, obtains sodium hydroxide-methanol solution；In the tetra-mouthfuls of reaction bulbs of 3000ml being equipped with reflux condenser, thermometer, constant pressure funnel, agitator being placed in ice-water bath, add tetranitro amine ethane-absolute methanol solution, treat that temperature is down to 0～5 DEG C, sodium hydroxide-the methanol solution prepared it is slowly added dropwise in reaction bulb, dropping stirs 1～4h after finishing, filter, rinse with absolute methanol, be filtered dry rear normal-temperature vacuum drying under reduced pressure, obtain white solid powder Na4TNAE·2H2O66.90g, productivity 80.67%(theoretical yield 82.93g).
Na4TNAE·2H2The density 2.006g/cm of O3；Initial decomposition temperature 200 DEG C, decomposition peak's temperature 258 DEG C；Na4C2N8H2O8·2H2O Elemental Analysis theory (%): C6.09, H1.52, N28.43；Measured value (%): C6.38, H1.06, N28.71；Na4The infrared analysis (KBr tabletting) of TNAE 2H2O: characteristic peak N-NO2: 1400,1395,1375,1385,1305,1275cm-1(s), C-H:2950,2920cm-1(w)；H2O:3400 (s), 1600cm-1W in () and document, report is basically identical；Nmr analysis (acetone, interior mark HMDS), hydrogen spectrum peak 5.84ppm, carbon spectrum peak 74.61ppm.
Claims (10)
1. the method synthesizing tetranitro amine tetrasodium salt, it is characterised in that: with glycoluril for raw material, react three steps through the nitration reaction of glycoluril, the hydrolysis of tetranitro glycoluril and the neutralization of tetranitro amine ethane and prepare tetranitro amine tetrasodium salt.
2. the method synthesizing tetranitro amine tetrasodium salt according to claim 1, it is characterised in that: the nitration reaction of described glycoluril, comprise the following steps:
(1) adding in reaction vessel by fuming nitric aicd, when cooling the temperature to 10 DEG C, add glycoluril, glycoluril obtains glycoluril-fuming nitric aicd solution after dissolving；
(2) temperature of glycoluril-fuming nitric aicd solution being down to 0～5 DEG C, drip acetic anhydride, dropping temperature is maintained at 0～5 DEG C；
(3) acetic anhydride finishes, and nitrated temperature is maintained at 0～5 DEG C, after nitration reaction 4h, raises nitrated temperature to 5～10 DEG C, continues nitrated 2～3h；Nitration reaction starts have precipitation to produce in 10min bottle, and nitrated thermograde progressively heats up；
(4) after nitration reaction, the material of step (3) is down to-10 DEG C～0 DEG C, material filtering in reaction bulb, obtains white solid tetranitro glycoluril, white solid tetranitro glycoluril dichloromethane is washed till neutrality, is immersed in dichloromethane stand-by.
3. the method synthesizing tetranitro amine tetrasodium salt according to claim 2, it is characterised in that: in the nitration reaction of described glycoluril, the mass ratio=1:10～1:50 that feeds intake of glycoluril and fuming nitric aicd, the volume ratio=1:2 of acetic anhydride and fuming nitric aicd.
4. the method synthesizing tetranitro amine tetrasodium salt according to claim 2, it is characterised in that: in the step (3) of the nitration reaction of described glycoluril, nitrated thermograde progressively heats up, that is: adopting 5 DEG C is gradient, heat up 5 DEG C again after keeping 2 hours, namely start nitrated temperature and be maintained at 0 DEG C, nitration reaction 2h, raise 5 DEG C, namely nitrated temperature rises to 5 DEG C, continues nitrated 2h, then raises 5 DEG C, namely nitrated temperature rises to 10 DEG C, then keeps 2～3 hours.
5. the method synthesizing tetranitro amine tetrasodium salt according to claim 1, it is characterised in that: the hydrolysis of described tetranitro glycoluril, comprise 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 DEG C；
(2) by the tetranitro glycoluril sucking filtration being immersed in dichloromethane, press dry after add hydrolysis, hydrolysis temperature 10 DEG C in the sodium hydrate aqueous solution of stirring；The ratio of tetranitro glycoluril and sodium hydroxide mole is: 1:20～1:5；
(3), after tetranitro glycoluril finishes, hydrolysis 0.5h is kept；
(4) reactant liquor of concentrated sulphuric acid neutralization procedure (3) it is slowly added to highly acid, neutral temperature 5 DEG C；
(5) add after absolute ether stirring extracts and filter, rinse white crystal sodium sulfate in sand core funnel with absolute ether, filtrate is layered, by upper strata ether extraction liquid dry more than the 4h of anhydrous sodium sulfate；
(6) ether extraction liquid in step (5) is carried out room temperature decompression distillation, ether is evaporated off, precipitates out to a large amount of solids, add the dichloromethane of 2-3 times of volume, be filtrated to get white solid tetranitro amine ethane；
(7) being dissolved in by tetranitro amine ethane equipped with in absolute methanol container, stirring, to dissolving, stands separatory, removes lower floor's impurity, and the supernatant loads in container stand-by.
6. the method synthesizing tetranitro amine tetrasodium salt according to claim 5, it is characterised in that: in the hydrolysis of described tetranitro glycoluril, the molar concentration 3.0mol/L-4.0mol/L of sodium hydrate aqueous solution, the mol ratio=1:1-1:2 of sodium hydroxide and concentrated sulphuric acid.
7. the method for described synthesis tetranitro amine tetrasodium salt according to claim 5, it is characterized in that: in the hydrolysis of tetranitro glycoluril, the method adopting pH reagent paper test pH-value carrys out controlled hydrolysis process, sodium hydrate aqueous solution pH value=14, finish the pH=7-10 of material after tetranitro glycoluril, concentrated sulphuric acid dropping finish after the pH=1 of material.
8. the method synthesizing tetranitro amine tetrasodium salt according to claim 5, it is characterized in that: also include between step (5) and step (6): the lower aqueous layer absolute ether extracting and demixing again after filtrate is layered, upper strata ether layer is incorporated in the ether extraction liquid of step (5).
9. the method synthesizing tetranitro amine tetrasodium salt according to claim 1, it is characterised in that: the neutralization reaction of described tetranitro amine ethane comprises the following steps:
(1) it is placed on adding in the reaction vessel of ice-water bath the absolute methanol liquid of tetranitro amine ethane, 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 slowly added dropwise to reaction bulb；
(3) stirring 1-4h after finishing, under filtration, room temperature, vacuum decompression dries, and obtains white solid tetranitro amine tetrasodium salt.
10. the method synthesizing tetranitro amine tetrasodium salt according to claim 9, it is characterised in that: in the neutralization reaction of described tetranitro amine ethane；The molar concentration 0.01mol/L-1.5mol/L of sodium hydroxide and absolute methanol；The mol ratio of tetranitro amine ethane and sodium hydroxide is 1:4.00～1:8.00.
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| CN108863839A (en) * | 2018-08-06 | 2018-11-23 | 湖北文理学院 | Alkali metal salt, preparation method and the high energy material of tenitramine base ethane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108863839A (en) * | 2018-08-06 | 2018-11-23 | 湖北文理学院 | Alkali metal salt, preparation method and the high energy material of tenitramine base ethane |
| CN108863839B (en) * | 2018-08-06 | 2021-03-26 | 湖北文理学院 | Alkali metal salt of tetranitraminoethane, preparation method thereof and high-energy material |
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