CN106748602B - Green gases propellant is hydrated pentazole metal salt and preparation method thereof - Google Patents
Green gases propellant is hydrated pentazole metal salt and preparation method thereof Download PDFInfo
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- CN106748602B CN106748602B CN201710055315.XA CN201710055315A CN106748602B CN 106748602 B CN106748602 B CN 106748602B CN 201710055315 A CN201710055315 A CN 201710055315A CN 106748602 B CN106748602 B CN 106748602B
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/04—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by auto-decomposition of single substances
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Abstract
The invention discloses the preparation method that a kind of green gases propellant is hydrated pentazole metal salt, green gases propellant of the invention is hydrated pentazole metal salt NaN5·H2The preparation method of O is simple and efficient, it is with metal inorganic frame structure, thermal decomposition characterization is carried out using thermodynamics mass spectrometry instrument to hydration pentazole metal salt obtained, it can be seen that, the good thermal stability of the structure, when being heated to 150 degree, a large amount of nitrogen is decomposed to give off rapidly, and generate without any gas flammability gas or toxic gas.The hydration pentazole sodium metal salt NaN of the present invention5·H2O is a kind of environmental type gas-forming agent of excellent combination property.
Description
Technical field
The invention belongs to energetic material technical field, it is related to a kind of green gases propellant hydration pentazole metal salt and its system
Preparation Method.
Background technology
Gas-forming agent is also known as gas generating agent, refers to the various substances that can generate gas after burning, belongs to solid propellant
A class.Since the propellant technique of sodium azide base gas-forming agent is more ripe, still it is mainly used for air bag at present
In, but the hypertoxicity of itself influences to use.The research of non-nitrine gas propellant becomes more and more active, including azole, piperazine class, guanidine
The gas-forming agent of the fuel agents such as class, azo.However these fuel agents cause danger or the extreme case of aging etc. under,
There may be hidden danger out of control of burning.Thus, it is imperative to develop green gases propellant.
Accordingly, it is desirable to provide a kind of green gases propellant hydration pentazole metal salt NaN5·H2The preparation method of O is to solve
The above problem.
Invention content
To solve the deficiencies in the prior art, the purpose of the present invention is to provide a kind of green gases propellant hydration pentazole gold
Belong to the preparation method of salt.
In order to realize that above-mentioned target, the present invention adopt the following technical scheme that：
A kind of preparation method of green gases propellant hydration pentazole metal salt, includes the following steps：
1) it, is equipped with the ethyl alcohol and water mixed solution of sodium metal salt, is equipped with the ethyl alcohol and water mixed solution of pentazole, wherein Na
The concentration of ion is identical with the concentration of pentazole；
2) ethyl alcohol and water mixed solution of the ethyl alcohol of sodium metal salt and water mixed solution and pentazole, are mixed to get second to mix
Close solution, wherein the ethyl alcohol and water mixed solution of sodium metal salt and the volume ratio of the ethyl alcohol of pentazole and water mixed solution are 1:1；
3), the second mixed solution for obtaining step 2) is ultrasonically treated, and third mixed solution is then obtained by filtration；
4), the third mixed solution that step 3) obtains is placed in climatic chamber and is stood, wherein in climatic chamber
Temperature is 40 DEG C -80 DEG C, and humidity 10%, solvent quickly volatilizees, until solvent volatilization 1/2；
5) temperature, is reduced to 10 DEG C, humidity 100%, solvent slowly volatilizees, and obtains hydration pentazole metal salt NaN5·
H2O。
Further, in step 1) in the ethyl alcohol and water mixed solution of sodium metal salt second alcohol and water volume ratio be 4~
6:6~4, the volume ratio of second alcohol and water is 4~6 in the ethyl alcohol and water mixed solution of pentazole in step 1):6~4.
Further, sodium metal salt is NaCl, Na in step 1)2SO4Or NaNO3。
Further, in step 1) Na ions a concentration of 1mol/L, a concentration of 1mol/L of pentazole.
Further, the time being ultrasonically treated in step 3) is 30 minutes.
Further, it is filtered with ultrafiltration membrane in step 3).
Further, pentazole in the ethyl alcohol and water mixed solution of pentazole is equipped in step 1) to be obtained by the cut-out of aryl pentazole
.
Further, in step 2) when having Precipitation in the second mixed solution or becoming cloudy, ethyl alcohol is added or goes
Ionized water is extremely clarified.
Advantageous effect：The preparation method of the green gases propellant hydration pentazole metal salt of the present invention is simple and efficient, and is had
There is metal inorganic frame structure, thermal decomposition table is carried out using thermodynamics-mass spectrometry instrument to hydration pentazole metal salt obtained
Sign, it can be seen that the good thermal stability of the structure decomposes to give off rapidly a large amount of nitrogen, and nothing when being heated to 150 degree
Any gas flammability gas or toxic gas generate.
The invention also discloses a kind of green gases propellant hydration pentazole metal salt NaN5·H2O is hydrated pentazole metal salt
NaN5·H2O has metal inorganic frame structure.
Advantageous effect：The green gases propellant hydration pentazole metal salt NaN of the present invention5·H2The good thermal stability of O,
When being heated to 150 degree, a large amount of nitrogen is decomposed to give off rapidly.No any gas flammability gas or toxic gas generate.This
The hydration pentazole sodium metal salt NaN of invention5·H2O is a kind of environmental type gas-forming agent of excellent combination property.
The invention also discloses hydration pentazole metal salt NaN5·H2O is used for gas-forming agent.
Advantageous effect：It is hydrated pentazole metal salt NaN5·H2O is used for gas-forming agent, and good thermal stability is being heated to
At 150 degree, a large amount of nitrogen is decomposed to give off rapidly.No any gas flammability gas or toxic gas generate.The water of the present invention
Close pentazole sodium metal salt NaN5·H2O is a kind of environmental type gas-forming agent of excellent combination property.
Figure of description
Fig. 1 is that the green gases propellant of the present invention is hydrated pentazole metal salt NaN5·H2The structural representation of O (100) crystal face
Figure；
Fig. 2 is that the green gases propellant of the present invention is hydrated pentazole metal salt NaN5·H2The structural representation of O (001) crystal face
Figure；
Fig. 3 is that the green gases propellant of the present invention is hydrated pentazole metal salt NaN5·H2The structural representation of O (100) crystal face
Figure；
Fig. 4 is hydration pentazole sodium metal salt NaN5·H2The thermogram of O；
Fig. 5 is the Mass Spectrometer Method figure of embodiment 1.
Specific implementation mode
Specific introduce is made to the present invention below in conjunction with specific embodiment.
It please participate in shown in Fig. 1, Fig. 2 and Fig. 3, inventor is cut off by aryl pentazole and obtains pentazole anion, after isolating and purifying
By the metathesis reaction with conventional sodium salt, the hydration pentazole sodium metal salt with stable metal inorganic frame structure is obtained
NaN5·H2O, the derivative have high energy, high generation heat, high gas generating amount, generate characteristics, these characteristics such as gas cleaning and want
It is substantially better than existing all kinds of gas-forming agents.
Pentazole anion N5 -It is the segment containing energy being all made of N element, can be analyzed to nitrogen under certain condition.With can
Combustion property gas-forming agent is compared, and there is no the danger for causing burning, while not needing or only needing a small amount of addition oxidant.Separately
Outside, compared with highly toxic azido compound, the toxicity of pentazole anion is relatively low.In short, the gas based on pentazole salt occurs
Agent has the advantages that high quick-fried, high generation heat, high gas generating amount, low-toxicity green, is the ideal chose of gas-forming agent.
Pentazole sodium metal salt NaN is hydrated in the present invention5·H2The synthesis of O is indicated with following the equation (I)：
Hydration pentazole sodium metal salt NaN is prepared by pentazole anion compound5·H2O includes the following steps：
A. match sodium metal salt (Na+) 1mol/L (1aq) ethyl alcohol and water mixed solution, metal salt anion Cl-, SO4 2-,
NO3 -Equal groups；Wherein, the volume ratio of ethanol/water mixed solution is 40%:60%~60%:40%.
B. match the ethyl alcohol and water mixed solution of a concentration of 1mol/L pentazoles；Wherein, the volume ratio of ethanol/water mixed solution is
40%:60%~60%:40%.
C. above-mentioned two parts of solution is mixed in equal volume, if having a small amount of Precipitation immediately after mixing or becoming cloudy, adds second
Alcohol or deionized water are extremely clarified；
D. ultrasound 30 minutes, use ultrafiltration membrance filter；
E. it is placed in climatic chamber and stands, humidity 10%, solvent quickly volatilizees, until solvent volatilization 1/2；Wherein,
Climatic chamber temperature is controlled at 40~80 DEG C.
F. temperature is reduced to 10 DEG C, humidity 100%, solvent slowly volatilizees, and has Crystallization.The crystal of acquisition is through monocrystalline
Diffraction characterizes, shown in structure following Fig. 1, Fig. 2 and Fig. 3, wherein hydration pentazole sodium metal salt NaN5·H2The mono-crystalline structures of O, Fig. 1
For (100) crystal face；Fig. 2 is (001) crystal face；Fig. 3 is (100) crystal face.
The present invention provides hydration pentazole sodium metal salt NaN5·H2The single crystal diffraction characterizing method of O and gas-forming agent
Thermodynamic property.
It please refers to shown in Fig. 4, metal inorganic frame structure is showed to obtained hydration pentazole sodium metal salt, using heat
Mechanics-mass spectrometry instrument carries out thermal decomposition characterization.The good thermal stability of the structure is rapid to decompose when being heated to 150 degree
Release a large amount of nitrogen.No any gas flammability gas or toxic gas generate.
Embodiment 1
The preparation of pentazole negative solution
It please refers to shown in Fig. 5,5mL methanol/acetonitrile is added in the three-necked flask of 25mL, is placed in low-temp reaction device and cools down
- 45 DEG C are cooled to, 0.191g 3,5- dimethyl -4- hydroxyaryls pentazoles (1mmol), by 0.966g tetrabutyl bromines is then added
Change ammonium (3mmol) to be dissolved in the mixed solution of 1mL deionized water+1mL methanol, be added in three-necked flask after being cooled to -45 DEG C.With
1.645g cerium ammonium nitrate (3mmol) and 0.1g Iron dichloride tetrahydrates (0.5mmol) are dissolved in 3mL deionized waters and 3mL afterwards
It in the mixed solution of methanol, is added drop-wise in three-necked flask after being cooled to -45 DEG C, after being stirred to react 30min, is warming up to 0 DEG C, continues
After reaction 2 hours, with Mass Spectrometer Method reaction solution, confirmation generates pentazole anion.Then it filters, rotates, soaked with 10ml methanol
Bubble, filters off insoluble by-product.Filtrate rotates drying, obtains pentazole anion solid.
Embodiment 2
By taking sodium chloride as an example, the crystal of pentazole sodium is prepared
Configure the ethanol/water (volume ratio 1 of sodium chloride NaC：1) mixed solution, a concentration of l mol/L；Configure the second of pentazole
Alcohol/water (volume ratio 1：1) mixed solution, a concentration of 1mol/L；Above-mentioned two parts of solution is mixed in equal volume, if having immediately after mixing
A small amount of Precipitation becomes cloudy, then adds ethyl alcohol or deionized water to clarification；Ultrasound 30 minutes, uses ultrafiltration membrance filter；It places
In climatic chamber, 70 DEG C of standings, humidity 10%, until solvent volatilization 1/2；Temperature is reduced to 10 DEG C, humidity 100%,
Solvent slowly volatilizees, and has Crystallization.
Embodiment 3
The volume ratio of two kinds of ethanol/water solutions in example 2 is adjusted to 60%：40%, climatic chamber temperature is set as
40 DEG C of standings, gained crystal are identical as example 2 by characterizing.
Embodiment 4
It is assumed that hydration pentazole sodium heat resolve under airtight vacuum environment, it is as follows to decompose equation：
It is hydrated pentazole sodium NaN5·H2When O decomposes generation, Na generates NaOH solids, separately has a small amount of hydrogen to supervene.By list
Position molal quantity calculates, and show that 1mol hydration pentazole sodium can generate 3mol gases；When being scaled unit mass, 1g is hydrated pentazole sodium can
Generate 0.6 liter of gas.
Embodiment 5
To common gas-forming agent NaN3, guanidine nitrate, nitroguanidine, the several compounds of 5- Aminotetrazoles by example 4 set
Airtight vacuum environment carry out thermal decomposition theory analysis, the results are shown in tables 1.The theoretical gas production of non-nitrine class gas-forming agent
Also higher, but be actually not easy to be completely decomposed into perfect condition, and full nitrogen anion this this problem is not present.It can from table 1
Go out, hydration pentazole sodium metal salt NaN of the invention5·H2O is a kind of environmental type gas-forming agent of excellent combination property.
Table 1
。
Claims (8)
1. a kind of preparation method of green gases propellant hydration pentazole metal salt, which is characterized in that include the following steps：
1) it, is equipped with the ethyl alcohol and water mixed solution of sodium metal salt, is equipped with the ethyl alcohol and water mixed solution of pentazole, wherein Na ions
Concentration it is identical with the concentration of pentazole；
2), that the ethyl alcohol and water mixed solution of the ethyl alcohol of sodium metal salt and water mixed solution and pentazole are mixed to get the second mixing is molten
Liquid, wherein the ethyl alcohol and water mixed solution of sodium metal salt and the volume ratio of the ethyl alcohol of pentazole and water mixed solution are 1:1；
3), the second mixed solution for obtaining step 2) is ultrasonically treated, and third mixed solution is then obtained by filtration；
4), the third mixed solution that step 3) obtains is placed in climatic chamber and is stood, wherein temperature in climatic chamber
It it is 40 DEG C -80 DEG C, humidity 10%, solvent quickly volatilizees, until solvent volatilization 1/2；
5) temperature, is reduced to 10 DEG C, humidity 100%, solvent slowly volatilizees, and obtains hydration pentazole metal salt NaN5·H2O。
2. the preparation method of green gases propellant hydration pentazole metal salt as described in claim 1, which is characterized in that step
1) volume ratio of second alcohol and water is 4~6 in the ethyl alcohol and water mixed solution of sodium metal salt in:6~4, the second of pentazole in step 1)
The volume ratio of second alcohol and water is 4~6 in alcohol and water mixed solution:6~4.
3. the preparation method of green gases propellant hydration pentazole metal salt as described in claim 1, which is characterized in that step
1) sodium metal salt is NaCl, Na in2SO4Or NaNO3。
4. the preparation method of green gases propellant hydration pentazole metal salt as described in claim 1, which is characterized in that step
1) a concentration of 1mol/L of Na ions in, a concentration of 1mol/L of pentazole.
5. the preparation method of green gases propellant hydration pentazole metal salt described in claim 1, which is characterized in that step 3)
The time of middle supersound process is 30 minutes.
6. the preparation method of green gases propellant hydration pentazole metal salt described in claim 1, which is characterized in that step 3)
It is middle to be filtered with ultrafiltration membrane.
7. the preparation method of green gases propellant hydration pentazole metal salt described in claim 1, which is characterized in that step 1)
Pentazole is cut off by aryl pentazole in the ethyl alcohol and water mixed solution of middle outfit pentazole obtains.
8. the preparation method of green gases propellant hydration pentazole metal salt described in claim 1, which is characterized in that step 2)
In when having Precipitation in the second mixed solution or becoming cloudy, ethyl alcohol or deionized water is added to clarifying.
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| CN113387902B (en) * | 2020-01-17 | 2023-02-24 | 吉林大学 | High-temperature high-pressure preparation method of limited-area high-density anhydrous alkali metal polymeric nitrogen Pmn21-NaN5 |
| FR3126708B1 (en) * | 2021-09-03 | 2023-09-01 | Arianegroup Sas | Process for making the pentazolate anion using a hypervalent iodine oxidant |
Citations (4)
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|---|---|---|---|---|
| CN1247525A (en) * | 1996-07-25 | 2000-03-15 | 科丹特技术公司 | Metal complexes for use as gas generants |
| WO2001038266A1 (en) * | 1999-11-26 | 2001-05-31 | Daicel Chemical Industries, Ltd. | Gas-generating agent composition |
| CN103736236A (en) * | 2014-01-13 | 2014-04-23 | 西安坚瑞安全应急设备有限责任公司 | Fire extinguishing composition containing heterocyclic compound |
| CN104583158A (en) * | 2012-10-18 | 2015-04-29 | 株式会社大赛璐 | Gas-generating-agent composition and gas generator using same |
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2017
- 2017-01-24 CN CN201710055315.XA patent/CN106748602B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1247525A (en) * | 1996-07-25 | 2000-03-15 | 科丹特技术公司 | Metal complexes for use as gas generants |
| WO2001038266A1 (en) * | 1999-11-26 | 2001-05-31 | Daicel Chemical Industries, Ltd. | Gas-generating agent composition |
| CN104583158A (en) * | 2012-10-18 | 2015-04-29 | 株式会社大赛璐 | Gas-generating-agent composition and gas generator using same |
| CN103736236A (en) * | 2014-01-13 | 2014-04-23 | 西安坚瑞安全应急设备有限责任公司 | Fire extinguishing composition containing heterocyclic compound |
Non-Patent Citations (2)
| Title |
|---|
| Theoretical studies on stability and pyrolysis mechanism of salts formed by N5- and metallic cations Na+, Fe2+ and Ni2+;Xueli Zhang，et al.;《Struct Chem》;20141203;第26卷;785-792 * |
| 多供电子基苯胺类化合物的合成及其芳基五唑衍生物稳定性;沈梦楠等;《精细化工》;20141231;第31卷(第12期);1531-1536 * |
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