CN106748602A - Green gases propellant hydration pentazole slaine and preparation method thereof - Google Patents
Green gases propellant hydration pentazole slaine and preparation method thereof Download PDFInfo
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- CN106748602A CN106748602A CN201710055315.XA CN201710055315A CN106748602A CN 106748602 A CN106748602 A CN 106748602A CN 201710055315 A CN201710055315 A CN 201710055315A CN 106748602 A CN106748602 A CN 106748602A
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- pentazole
- slaine
- mixed solution
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
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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
Abstract
The invention discloses the preparation method that a kind of green gases propellant is hydrated pentazole slaine, green gases propellant hydration pentazole slaine NaN of the invention5·H2The preparation method of O is simply efficient, it has metal inorganic frame structure, thermal decomposition sign is carried out using thermodynamics mass spectrometry instrument to obtained hydration pentazole slaine, it can be seen that, the good thermal stability of the structure, when being heated to 150 degree, substantial amounts of nitrogen is decomposed to give off rapidly, and produce without any gas flammability gas or toxic gas.Hydration pentazole sodium slaine NaN of the 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 hydration of green gases propellant pentazole slaine and its system
Preparation Method.
Background technology
Gas-forming agent, also known as gas generating agent, refers to the various materials that gas can be produced after burning, and belongs to solid propellant
A class.Because the propellant technique of sodium azide base gas-forming agent is more ripe, air bag is still mainly used at present
In, but itself hypertoxicity influence use.The research of non-nitrine gas propellant is increasingly active, including azole, piperazine class, guanidine
The gas-forming agent of the fuel agents such as class, azo.But these fuel agents cause danger or the extreme case of aging grade under,
There may be burning hidden danger out of control.Thus, develop green gases propellant imperative.
Accordingly, it is desirable to provide a kind of green gases propellant hydration pentazole slaine NaN5·H2The preparation method of O is solving
Above mentioned problem.
The content of the invention
To solve the deficiencies in the prior art, it is an object of the invention to provide a kind of green gases propellant hydration pentazole gold
Belong to the preparation method of salt.
In order to realize above-mentioned target, the present invention is adopted the following technical scheme that：
A kind of green gases propellant is hydrated the preparation method of pentazole slaine, comprises the following steps：
1) ethanol and water mixed solution of sodium slaine, are equipped with, the ethanol and water mixed solution of pentazole is equipped with, wherein, Na
The concentration of ion is identical with the concentration of pentazole；
2) ethanol and water mixed solution of the ethanol and water mixed solution of sodium slaine and pentazole, are mixed to get into second to mix
Solution is closed, wherein, the volume ratio of the ethanol and water mixed solution of sodium slaine and the ethanol of pentazole and water mixed solution is 1:1；
3), by step 2) the second mixed solution for obtaining is ultrasonically treated, is then filtrated to get the 3rd mixed solution；
4), by step 3) the 3rd mixed solution that obtains stands in being placed on climatic chamber, wherein, in climatic chamber
Temperature is 40 DEG C -80 DEG C, and humidity is 10%, and 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 slaine NaN5·
H2O。
Further, step 1) in the ethanol of sodium slaine and the volume ratio of second alcohol and water in water mixed solution for 4~
6:6~4, step 1) in the ethanol of pentazole and the volume ratio of second alcohol and water in water mixed solution be 4~6:6~4.
Further, step 1) in sodium slaine be NaCl, Na2SO4Or NaNO3。
Further, step 1) in the concentration of Na ions be 1mol/L, the concentration of pentazole is 1mol/L.
Further, step 3) in ultrasonically treated time be 30 minutes.
Further, step 3) in filtered with milipore filter.
Further, step 1) in be equipped with pentazole ethanol and water mixed solution in pentazole by aryl pentazole cut-out obtain
.
Further, step 2) in when having Precipitation or becoming cloudy in the second mixed solution, add and ethanol or go
Ionized water is extremely clarified.
Beneficial effect：The preparation method of green gases propellant hydration pentazole slaine of the invention is simply efficient, its tool
There is metal inorganic frame structure, thermal decomposition table is carried out using thermodynamics-mass spectrometry instrument to obtained hydration pentazole slaine
Levy, it can be seen that the good thermal stability of the structure, when being heated to 150 degree, substantial amounts of nitrogen, and nothing are decomposed to give off rapidly
Any gas flammability gas or toxic gas are produced.
The invention also discloses a kind of green gases propellant hydration pentazole slaine NaN5·H2O, is hydrated pentazole slaine
NaN5·H2O has metal inorganic frame structure.
Beneficial effect：Green gases propellant hydration pentazole slaine NaN of the invention5·H2The good thermal stability of O,
When being heated to 150 degree, substantial amounts of nitrogen is decomposed to give off rapidly.Produced without any gas flammability gas or toxic gas.This
The hydration pentazole sodium slaine NaN of invention5·H2O is a kind of environmental type gas-forming agent of excellent combination property.
The invention also discloses hydration pentazole slaine NaN5·H2O is used for gas-forming agent.
Beneficial effect：Hydration pentazole slaine NaN5·H2O is used for gas-forming agent, and good thermal stability is being heated to
At 150 degree, substantial amounts of nitrogen is decomposed to give off rapidly.Produced without any gas flammability gas or toxic gas.Water of the invention
Close pentazole sodium slaine NaN5·H2O is a kind of environmental type gas-forming agent of excellent combination property.
Figure of description
Fig. 1 is green gases propellant of the invention hydration pentazole slaine NaN5·H2The structural representation of O (100) crystal face
Figure；
Fig. 2 is green gases propellant of the invention hydration pentazole slaine NaN5·H2The structural representation of O (001) crystal face
Figure；
Fig. 3 is green gases propellant of the invention hydration pentazole slaine NaN5·H2The structural representation of O (100) crystal face
Figure；
Fig. 4 is hydration pentazole sodium slaine NaN5·H2The thermal analysis curue of O；
Fig. 5 is the Mass Spectrometer Method figure of embodiment 1.
Specific embodiment
Make specific introduction to the present invention below in conjunction with specific embodiment.
Please participate in shown in Fig. 1, Fig. 2 and Fig. 3, inventor obtains pentazole anion by the cut-out of aryl pentazole, after isolating and purifying
By the metathesis reaction with conventional sodium salt, the hydration pentazole sodium slaine of the metal inorganic frame structure with stabilization is obtained
NaN5·H2O, the derivative has high energy, generation gas generating amount hot, high high, produces the characteristics such as gas cleaning, and these characteristics will
It is substantially better than existing all kinds of gas-forming agents.
Pentazole anion N5 -It is the fragment containing energy being all made up of N element, nitrogen is can be analyzed under certain condition.With can
Combustion property gas-forming agent is compared, in the absence of the danger for causing burning, without the need for or only need a small amount of addition oxidant.Separately
Outward, compared with highly toxic azido compound, the toxicity of pentazole anion is relatively low.In a word, the gas based on pentazole salt occurs
Agent, has the advantages that quick-fried, high generation gas generating amount hot, high high, low-toxicity green, is the ideal chose of gas-forming agent.
Pentazole sodium slaine NaN is hydrated in the present invention5·H2The synthesis of O is represented with the equation below (I)：
Hydration pentazole sodium slaine NaN is prepared by pentazole negative ionization compound5·H2O comprises the following steps：
A. sodium slaine (Na is matched somebody with somebody+) 1mol/L (1aq) ethanol and water mixed solution, metal salt anion is Cl-, SO4 2-,
NO3 -Deng group；Wherein, the volume ratio of ethanol/water mixed solution is 40%:60%~60%:40%.
B. it is the ethanol and water mixed solution of 1mol/L pentazoles with concentration；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 there is a small amount of Precipitation immediately after mixing or become cloudy, plus 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 control is 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 is characterized, shown in structure below figure 1, Fig. 2 and Fig. 3, wherein, hydration pentazole sodium slaine NaN5·H2The mono-crystalline structures of O, Fig. 1
It is (100) crystal face；Fig. 2 is (001) crystal face；Fig. 3 is (100) crystal face.
The invention provides hydration pentazole sodium slaine NaN5·H2The single crystal diffraction characterizing method of O and gas-forming agent
Thermodynamic property.
Refer to shown in Fig. 4, metal inorganic frame structure is showed to obtained hydration pentazole sodium slaine, using heat
Mechanics-mass spectrometry instrument carries out thermal decomposition sign.The good thermal stability of the structure is rapid to decompose when being heated to 150 degree
Release substantial amounts of nitrogen.Produced without any gas flammability gas or toxic gas.
Embodiment 1
The preparation of pentazole negative solution
Refer to shown in Fig. 5,5mL methyl alcohol/acetonitrile is added in the there-necked flask of 25mL, be placed in low-temp reaction device and lower the temperature
- 45 DEG C are cooled to, 0.191g 3,5- dimethyl -4- hydroxyaryls pentazole (1mmol) are then added, by 0.966g tetrabutyl bromines
Change ammonium (3mmol) to be dissolved in the mixed solution of 1mL deionized water+1mL methyl alcohol, after being cooled to -45 DEG C in addition there-necked flask.With
1.645g cerium ammoniums nitrate (3mmol) and 0.1g Iron dichloride tetrahydrates (0.5mmol) are dissolved in 3mL deionized waters and 3mL afterwards
In the mixed solution of methyl alcohol, it is added drop-wise in there-necked flask after being cooled to -45 DEG C, after stirring reaction 30min, is warming up to 0 DEG C, is continued
After reaction 2 hours, with Mass Spectrometer Method reaction solution, confirmation generates pentazole anion.Then filter, rotate, soaked with 10ml methyl alcohol
Bubble, filters off insoluble accessory substance.Filtrate rotates drying, obtains pentazole anion solid.
Embodiment 2
By taking sodium chloride as an example, the crystal of pentazole sodium is prepared
Ethanol/water (the volume ratio 1 of configuration sodium chloride NaC：1) mixed solution, concentration is l mol/L；Configure the second of pentazole
Alcohol/water (volume ratio 1：1) mixed solution, concentration is 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 add ethanol or deionized water to clarification；Ultrasound 30 minutes, uses ultrafiltration membrance filter；Place
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 to
40 DEG C of standings, gained crystal is identical with example 2 by characterizing.
Embodiment 4
It is assumed that hydration pentazole sodium heat resolve under airtight vacuum environment, it is as follows that it decomposes equation：
Hydration pentazole sodium NaN5·H2O is decomposed when occurring, Na generation NaOH solids, separately has a small amount of hydrogen to supervene.By list
Position molal quantity is calculated, and show that 1mol hydration pentazole sodium can produce 3mol gases；When being scaled unit mass, 1g hydration pentazole sodium can
Produce 0.6 liter of gas.
Embodiment 5
To common gas-forming agent NaN3, guanidine nitrate, nitroguanidine, the several compounds of 5- Aminotetrazoles set by example 4
Airtight vacuum environment carry out thermal decomposition theory analysis, its result is listed in table 1.The theoretical gas production of non-nitrine class gas-forming agent
Also it is higher, but be actually difficult to be completely decomposed into perfect condition, and full nitrogen anion this do not exist this problem.Can from table 1
Go out, hydration pentazole sodium slaine NaN of the invention5·H2O is a kind of environmental type gas-forming agent of excellent combination property.
Table 1
Claims (10)
1. a kind of green gases propellant is hydrated the preparation method of pentazole slaine, it is characterised in that comprise the following steps：
1) ethanol and water mixed solution of sodium slaine, are equipped with, the ethanol and water mixed solution of pentazole is equipped with, wherein, Na ions
Concentration it is identical with the concentration of pentazole；
2), that the ethanol and water mixed solution of the ethanol and water mixed solution of sodium slaine and pentazole are mixed to get into the second mixing is molten
Liquid, wherein, the volume ratio of the ethanol and water mixed solution of sodium slaine and the ethanol of pentazole and water mixed solution is 1:1；
3), by step 2) the second mixed solution for obtaining is ultrasonically treated, is then filtrated to get the 3rd mixed solution；
4), by step 3) the 3rd mixed solution that obtains stands in being placed on climatic chamber, wherein, temperature in climatic chamber
It it is 40 DEG C -80 DEG C, humidity is 10%, and 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 slaine NaN5·H2O。
2. green gases propellant as claimed in claim 1 is hydrated the preparation method of pentazole slaine, it is characterised in that step
1) volume ratio of second alcohol and water is 4~6 in the ethanol and water mixed solution of sodium slaine in:6~4, step 1) in pentazole second
The volume ratio of second alcohol and water is 4~6 in alcohol and water mixed solution:6~4.
3. green gases propellant as claimed in claim 1 is hydrated the preparation method of pentazole slaine, it is characterised in that step
1) sodium slaine is NaCl, Na in2SO4Or NaNO3。
4. green gases propellant as claimed in claim 1 is hydrated the preparation method of pentazole slaine, it is characterised in that step
1) concentration of Na ions is 1mol/L in, and the concentration of pentazole is 1mol/L.
5. the green gases propellant described in claim 1 is hydrated the preparation method of pentazole slaine, it is characterised in that step 3)
In ultrasonically treated time be 30 minutes.
6. the green gases propellant described in claim 1 is hydrated the preparation method of pentazole slaine, it is characterised in that step 3)
It is middle to be filtered with milipore filter.
7. the green gases propellant described in claim 1 is hydrated the preparation method of pentazole slaine, it is characterised in that step 1)
Pentazole is cut off by aryl pentazole and obtained in the ethanol and water mixed solution of middle outfit pentazole.
8. the green gases propellant described in claim 1 is hydrated the preparation method of pentazole slaine, it is characterised in that step 2)
In when having Precipitation or becoming cloudy in the second mixed solution, add ethanol or deionized water to clarifying.
9. green gases propellant is hydrated pentazole slaine NaN5·H2O, it is characterised in that hydration pentazole slaine
NaN5·H2O has metal inorganic frame structure.
10. pentazole slaine NaN is hydrated5·H2O is used for gas-forming agent.
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| CN201710055315.XA CN106748602B (en) | 2017-01-24 | 2017-01-24 | Green gases propellant is hydrated pentazole metal salt and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113387902A (en) * | 2020-01-17 | 2021-09-14 | 吉林大学 | High-temperature high-pressure preparation method of limited-area high-density anhydrous alkali metal polymeric nitrogen Pmn21-NaN5 |
| WO2023031552A1 (en) * | 2021-09-03 | 2023-03-09 | Arianegroup Sas | Method for producing the pentazolate anion using a hypervalent iodine oxidant |
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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 |
-
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 |
|---|
| XUELI ZHANG，ET AL.: "Theoretical studies on stability and pyrolysis mechanism of salts formed by N5- and metallic cations Na+, Fe2+ and Ni2+", 《STRUCT CHEM》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113387902A (en) * | 2020-01-17 | 2021-09-14 | 吉林大学 | High-temperature high-pressure preparation method of limited-area high-density anhydrous alkali metal polymeric nitrogen Pmn21-NaN5 |
| 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 |
| WO2023031552A1 (en) * | 2021-09-03 | 2023-03-09 | Arianegroup Sas | Method for producing the pentazolate anion using a hypervalent iodine oxidant |
| FR3126708A1 (en) * | 2021-09-03 | 2023-03-10 | Arianegroup Sas | Process for making pentazolate anion using hypervalent iodine oxidant |
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