CN108101722A - A kind of Hexanitrohexaazaisowurtzitane and nitroguanidine cocrystallized explosive and preparation method thereof - Google Patents
A kind of Hexanitrohexaazaisowurtzitane and nitroguanidine cocrystallized explosive and preparation method thereof Download PDFInfo
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- CN108101722A CN108101722A CN201711382764.1A CN201711382764A CN108101722A CN 108101722 A CN108101722 A CN 108101722A CN 201711382764 A CN201711382764 A CN 201711382764A CN 108101722 A CN108101722 A CN 108101722A
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- nitroguanidine
- hexanitrohexaazaisowurtzitane
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/36—Compositions containing a nitrated organic compound the compound being a nitroparaffin
- C06B25/38—Compositions containing a nitrated organic compound the compound being a nitroparaffin with other nitrated organic compound
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Abstract
The invention discloses a kind of Hexanitrohexaazaisowurtzitanes and nitroguanidine cocrystallized explosive and preparation method thereof.Preparation method is：Nitroguanidine is added in solvent methanol first, 45 55 degree, after stirring and dissolving is warming up to, nitroguanidine saturated solution is obtained by filtration.Solution is maintained at 45 55 DEG C, Hexanitrohexaazaisowurtzitane is added in nitroguanidine saturated solution, stirring and dissolving obtains Hexanitrohexaazaisowurtzitane and nitroguanidine saturated crystallization solution.Then 30 60min are mixed in the case where being maintained at 40 50 DEG C for mixed crystallization solution obtained by previous step, stop stirring and be progressively cooled to room temperature, stand 12 days, solvent volatilizees, nucleus, which is formed and grown up, is precipitated crystal, filtration drying obtains CL 20/NQ eutectics, and the ratio of CL 20 and NQ is 1 in obtained eutectic：2.The thermal behaviors such as CL 20/NQ cocrystallized explosives prepared by the present invention, the fusing and decomposition of explosive are regulated, and the cocrystallized explosive of gained realizes effectively drop sense while higher energy density is possessed, and has preferable application prospect in high-energy insensitive powder charge field.
Description
Technical field
The invention belongs to energetic material fields, and in particular to Hexanitrohexaazaisowurtzitane (CL-20) and nitroguanidine (NQ)
The preparation method of cocrystallized explosive, the present invention have preferable application prospect in high-energy insensitive explosive.
Background technology
Hexanitrohexaazaisowurtzitane (HNIW, also known as CL-20) is a kind of more ammonium nitrate compounds of novel solid caged, is
One of energy highest, comprehensive performance single chmical compound explosive the most good at present, in high-performance, low characteristic signal propellant and high energy
Application in composite explosives has carried out deeply and systematic research.But there are a common problem in its application process, i.e.,
Since the sensitivity of CL-20 is higher, its application in the low sense ammunition of high energy is limited.Eutectic is widely used in as a kind of early stage
Technology in drug molecule modification, in recent years since it can overcome common modifications method that cannot change the excellent of explosive internal composition
Gesture tends to achieve the effect that structure adjusting explosive property, thus has more exploration application in explosive modification field.
Nitroguanidine (NQ) is as a kind of common energetic material, as propellant powder, propellant and Explosives, extensive use
In the energetic materials application field such as explosive wastewater, density and explosion velocity are relatively low, but the extremely low (H of sensitivity50<320cm), so frequently as blunt
Feel explosive to use.NH groups containing electron deficient in nitroguanidine molecule, the nitryl group containing electron rich in CL-20 molecules.Such as
CL-20 and NQ can be attached in same structure cell by fruit by eutectic technology, then have very likely both overcome the high sensitivity of CL-20
Problem, while solve the problems, such as the low energy low-density of NQ.Yet with materialization caused by the two chemical constitution and molecular weight difference
It is difficult to select suitable ratio and solvent, eutectic is obtained by conventional solvent method for nature difference.It is total at present on CL-20/NQ
The preparation of brilliant explosive there is no disclosure.
The content of the invention
Present invention aims to overcome that the deficiencies in the prior art, provide a kind of Hexanitrohexaazaisowurtzitane and nitro
Guanidine cocrystallized explosive and preparation method thereof, specifically includes following technical scheme：
1. the preparation of Hexanitrohexaazaisowurtzitane and nitroguanidine saturated crystallization solution
Nitroguanidine is added in solvent, is warming up to 45-55 degree, after stirring and dissolving, nitroguanidine saturated solution is obtained by filtration.It is molten
Liquid is maintained at 45-55 DEG C, Hexanitrohexaazaisowurtzitane is added in nitroguanidine saturated solution, stirring and dissolving obtains hexanitro
Hexaazaisopen wootz alkyl and nitroguanidine saturated crystallization solution.
2. the preparation of Hexanitrohexaazaisowurtzitane and nitroguanidine cocrystallized explosive
30-60min is mixed in the case where being maintained at 40-50 DEG C for mixed crystallization solution obtained by previous step, mixing speed is protected
50-100 revs/min is held, then stops stirring and is progressively cooled to room temperature, stand 1-2 days, solvent volatilization, nucleus is formed and grown up
Crystal is precipitated, filtration drying obtains CL-20/NQ eutectics, and the ratio of CL-20 and NQ is 1 in obtained eutectic：2.
Further technical solution is that the rate of charge of middle CL-20 and NQ is 1 in the step 1：2, and CL-20 is brilliant for ε
Type sterling, recrystallisation solvent are methanol；The specific procedure that progressively cools down in the step 2 is to reduce by 5~8 degrees Celsius every time by former temperature
Keep the temperature 2 it is small when, until be reduced to room temperature.
Compared with prior art, the beneficial effects of the present invention are the CL-20/NQ eutectics that this method is prepared melt
The thermal behaviors such as change and thermal decomposition, compared with melting the CL-20 and NQ that are carried out at the same time with decomposition behavior, eutectic is before thermal decomposition behavior
There is apparent fusion process to occur, i.e., then may be under the conditions of excellent detonation property be maintained with relatively low fusing point, sensitivity
Also it is decreased obviously.From there through the eutectic of CL-20 and NQ, the thermal behaviors such as fusing of explosive are regulated, and the eutectic of gained is fried
Medicine realizes effectively drop sense while higher energy density is possessed, before having preferable application in high-energy insensitive powder charge field
Scape.
Description of the drawings
Fig. 1 is the preparation technology flow chart of Hexanitrohexaazaisowurtzitane and nitroguanidine cocrystallized explosive in the present invention.
Fig. 2 is the crystal structure figure of Hexanitrohexaazaisowurtzitane and nitroguanidine cocrystallized explosive in the present invention.
Fig. 3 is Hexanitrohexaazaisowurtzitane and nitroguanidine cocrystallized explosive in the present invention, CL-20, NQ one pack system and
The DSC figures of blend.
Fig. 4 is Hexanitrohexaazaisowurtzitane and nitroguanidine cocrystallized explosive in the present invention, CL-20, NQ one pack system and
The infrared spectrogram of its blend.
Specific embodiment
With reference to embodiment, the present invention is described further.
Embodiment 1：
40ml methanol is added in there-necked flask, precise 52mg nitroguanidines are added in there-necked flask, risen under agitation
Temperature is to 45 DEG C, until nitroguanidine is completely dissolved, hot saturated solution is obtained by filtration.It keeps under 45 DEG C of states, adds in six azepine of hexanitro
Different 5 hereby alkane 109.5mg are stirred to after all dissolving and are continued that 60min is mixed.Then solution is transferred in beaker while hot,
Stop stirring and be cooled to 40 DEG C, keep temperature 2h, according to program of the heat preservation 2 after each 5 DEG C of reduction when small, be finally down to room temperature
20 DEG C, it is statically placed in ventilation 1-2 days, solvent volatilization nucleus, which is formed and grown up, is precipitated crystal, and filtration drying obtains CL-20/NQ and is total to
It is brilliant.
Embodiment 2：
80ml methanol is added in there-necked flask, precise 104mg nitroguanidines are added in there-necked flask, risen under agitation
Temperature is to 50 DEG C, until nitroguanidine is completely dissolved, hot saturated solution is obtained by filtration.It keeps under 50 DEG C of states, adds in six azepine of hexanitro
Different 5 hereby alkane 218mg are stirred to after all dissolving and are continued that 60min is mixed.Then solution is transferred in beaker while hot, is stopped
Only stirring is cooled to 45 DEG C, keeps temperature 2h, according to program of the heat preservation 2 after each 5 DEG C of reduction when small, is finally down to room temperature 20
DEG C, it is statically placed in ventilation 1-2 days, solvent volatilization nucleus, which is formed and grown up, is precipitated crystal, and filtration drying obtains CL-20/NQ eutectics.
Embodiment 3：
40ml methanol is added in there-necked flask, precise 120mg nitroguanidines are added in there-necked flask, risen under agitation
Temperature is to 55 DEG C, until nitroguanidine is completely dissolved, hot saturated solution is obtained by filtration.It keeps under 55 DEG C of states, adds in six azepine of hexanitro
Different 5 hereby alkane 251mg are stirred to after all dissolving and are continued that 60min is mixed.Then solution is transferred in beaker while hot, is stopped
Only stirring is cooled to 50 DEG C, keeps temperature 2h, according to program of the heat preservation 2 after each 5 DEG C of reduction when small, is finally down to room temperature 20
DEG C, it is statically placed in ventilation 1-2 days, solvent volatilization nucleus, which is formed and grown up, is precipitated crystal, and filtration drying obtains CL-20/NQ eutectics.
As shown in Figure 1, the system for Hexanitrohexaazaisowurtzitane of the present invention (CL-20) and nitroguanidine (NQ) cocrystallized explosive
Standby process flow chart.
As shown in Fig. 2, the crystal structure for Hexanitrohexaazaisowurtzitane (CL-20) and nitroguanidine (NQ) cocrystallized explosive
Figure, as seen from the figure, the eutectic is by CL-20 and NQ according to 1:2 molar ratio is combined into, and mainly passes through the nitroxide on CL-20
It is formed with the hydrogen bond action for the hydrogen atom being connected on NQ with nitrogen-atoms.
As shown in figure 3, for Hexanitrohexaazaisowurtzitane (CL-20) and nitroguanidine (NQ) cocrystallized explosive in the present invention,
The DSC figures of CL-20, NQ one pack system.From the figure 3, it may be seen that being different from CL-20 and NQ, there is fusing row at 200 DEG C or so in eutectic
To be substantially reduced compared with CL-20 and NQ fusing points, it was demonstrated that the thermal behavior of the shape molecular pairs of eutectic, which has, to be significantly improved.
As shown in figure 4, for Hexanitrohexaazaisowurtzitane (CL-20) and nitroguanidine (NQ) cocrystallized explosive in the present invention,
The infrared spectrogram of CL-20, NQ one pack system.As shown in Figure 4, compared with CL-20, NQ and CL-20 and the blend of NQ, it is prepared
CL-20/NQ eutectics not only it is original absorption peak position and intensity have absworption peak that is offset, while having also appeared new, it was demonstrated that
The interior molecules bonding action of CL-20/NQ eutectics and different, the formation of intermolecular hydrogen bonding between CL-20 and NQ of common blend,
Directly resulting in the arrangement of its interior molecules tends to ordering, finally directly affects its physico-chemical property.
As shown in table 1, it is the impact sensitivity data of CL-20, NQ and CL-20/NQ eutectic.Using drop weight method in identical test
Under the conditions of (5kg drops hammer, and ignition probability is more than 50%, and test number (TN) 25 is sent out) impact sensitivity inspection is carried out to two kinds of one-components and eutectic
It surveys, is understood by data in table compared with CL-20 simple substance, the CL-20/NQ eutectic sensitivity for preparing gained is substantially reduced, drop sense effect
Substantially.
The impact sensitivity table of 1 CL-20, NQ and CL-20/NQ eutectic of table
| Sample | CL-20 | NQ | CL-20/NQ eutectics |
| Impact sensitivity H50(cm) | 19 | 177 | 61 |
Claims (4)
1. the preparation method of a kind of Hexanitrohexaazaisowurtzitane and nitroguanidine cocrystallized explosive, which is characterized in that including following
Step：
(1) nitroguanidine is added in solvent, is warming up to 45-55 degree, after stirring and dissolving, nitroguanidine saturated solution is obtained by filtration, it is molten
Liquid temperature degree is maintained at 45-55 DEG C, Hexanitrohexaazaisowurtzitane is added in nitroguanidine saturated solution, stirring and dissolving obtains six
The saturated crystallization solution of nitro hexaazaisopen wootz alkyl and nitroguanidine.
(2) 30-60min is mixed in the case where being maintained at 45-55 DEG C for mixed crystallization solution obtained by previous step, mixing speed is kept
50-100 revs/min, then stop stirring and be progressively cooled to room temperature, specific cooling process is to reduce by 5~8 every time by former temperature to take the photograph
When family name's degree heat preservation 2 is small, until being reduced to room temperature, 1-2 days are stood, solvent volatilization, nucleus, which is formed and grown up, is precipitated crystal, crosses and is filtered dry
It is dry to obtain Hexanitrohexaazaisowurtzitane and nitroguanidine eutectic.
2. the preparation method of Hexanitrohexaazaisowurtzitane according to claim 1 and nitroguanidine cocrystallized explosive, special
Sign is that the molar ratio of middle Hexanitrohexaazaisowurtzitane and nitroguanidine is 1 in the step 1：2, raw material hexanitro
Hexaazaisopen wootz alkyl is ε crystal form sterlings, and recrystallisation solvent is methanol.
3. a kind of Hexanitrohexaazaisowurtzitane and nitroguanidine cocrystallized explosive, it is characterised in that：Six azepine of hexanitro is different
5 hereby alkane and when nitroguanidine cocrystallized explosive be prepared by the preparation method of claim 1 or 2.
4. Hexanitrohexaazaisowurtzitane according to claim 3 and nitroguanidine cocrystallized explosive, it is characterised in that：Six nitre
Base hexaazaisopen wootz alkyl and nitroguanidine are according to 1:2 molar ratios are combined by intermolecular hydrogen bonding.
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Cited By (1)
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| CN109535096A (en) * | 2018-12-25 | 2019-03-29 | 西安近代化学研究所 | A kind of eutectic method based on resonance auxiliary |
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| CN103396274A (en) * | 2013-08-16 | 2013-11-20 | 中国工程物理研究院化工材料研究所 | Preparation method for hexanitrohexaazaisowurtzitane and m-dinitrobenzene co-crystallized explosive |
| CN104860786A (en) * | 2015-06-04 | 2015-08-26 | 西安近代化学研究所 | Preparation method of hexanitrohexaazaisowurtzitane and 2,5-dinitrotoluene eutectic explosive |
| US9701592B1 (en) * | 2015-08-06 | 2017-07-11 | The United States Of America As Represented By The Secretary Of The Army | Single-step production method for nano-sized energetic cocrystals by bead milling and products thereof |
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2017
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| CN103396274A (en) * | 2013-08-16 | 2013-11-20 | 中国工程物理研究院化工材料研究所 | Preparation method for hexanitrohexaazaisowurtzitane and m-dinitrobenzene co-crystallized explosive |
| CN104860786A (en) * | 2015-06-04 | 2015-08-26 | 西安近代化学研究所 | Preparation method of hexanitrohexaazaisowurtzitane and 2,5-dinitrotoluene eutectic explosive |
| US9701592B1 (en) * | 2015-08-06 | 2017-07-11 | The United States Of America As Represented By The Secretary Of The Army | Single-step production method for nano-sized energetic cocrystals by bead milling and products thereof |
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| CN109535096A (en) * | 2018-12-25 | 2019-03-29 | 西安近代化学研究所 | A kind of eutectic method based on resonance auxiliary |
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Application publication date: 20180601 |