CN109574774A - A kind of organic inorganic hybridization energetic material and preparation method thereof - Google Patents
A kind of organic inorganic hybridization energetic material and preparation method thereof Download PDFInfo
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- CN109574774A CN109574774A CN201811520682.3A CN201811520682A CN109574774A CN 109574774 A CN109574774 A CN 109574774A CN 201811520682 A CN201811520682 A CN 201811520682A CN 109574774 A CN109574774 A CN 109574774A
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0008—Compounding the ingredient
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Abstract
The invention discloses a kind of organic inorganic hybridization energetic materials and preparation method thereof, the energetic material is by organic oxidizing agent and inorganic metal fuel composition, wherein organic oxidizing agent is selected from polytetrafluoroethylene (PTFE), fluorinated graphene, perfluorocarboxylic acid, any one or a few in vinylidene-chlorotrifluoroethylene 1:1 copolymer and vinylidene-chlorotrifluoroethylene 1:4 copolymer, the inorganic metal fuel is selected from aluminium, magnesium, boron, any one or a few in silicon and titanium, energetic material is assembled by way of organic inorganic hybridization, control the microstructure of organic oxidizing agent and inorganic metal fuel and the uniformity of component, form organic inorganic hybridization energetic material, obtain the energetic material of high-energy density.
Description
Technical field
The present invention relates to energetic material technical fields, and in particular to a kind of organic inorganic hybridization energetic material and its preparation side
Method is mainly used for the preparation of high energy energetic material.
Background technique
Energetic material is the energy that weapon system is promoted and injured, and is had great importance for weapon property development.Its
In how to improve energetic material high-energy density it is very crucial for the development and weapon performance boost of energetic material.
CHON explosive is most widely used in weapons and ammunitions, but because the atomic mass of its element is small, while by its element
Type, atom pile up the limitation of mode and chemical bond energy, and the space for improving density and energy is limited.The existing CHON explosive limit is close
Degree is 2.3g/cm3, detonation property improves potential and there was only 30%, it is difficult to meet the following weapon to high-energy density energetic material
Demand.In order to improve the energy density of CHON explosive, researcher introduces new element in CHON explosive molecules, such as nonmetallic (F,
Cl), metallic element (Si, B) etc..For F compared with O, oxidant is stronger, and atomic weight is bigger, therefore replaces O that density can be improved with F
And energy.Two chloro amidos are introduced into HMX, and density (4.7%), energy (detonation pressure improves 26.7%) and the specific impulse that HMX can be improved (mention
It is high 4.8%).US Naval Research Laboratory separates in the middle part of the cyclic structure of similar ammonium nitrate explosive (such as HMX, RDX) into NF2, with
This improves energy, synthesized 3,3,7,7- tetra- (difluoro amino) it is octahydro -1,5- dinitro -1,5- diaza octane
(HNFX), but yield is only about 1%.Energy density can be significantly improved by introducing fluorine element in the molecule, however synthesize difficulty it is big,
Product stability is poor, can not obtain available high-energy energetic material.
With nonmetallic phase ratio, metallic element density is bigger, and chemical bond energy is higher, in the energy density side for promoting energetic material
Face has great potential.Early stage introduces the Azide of the formation such as heavy metal element such as lead (Pb), copper (Cu), mercury (Hg) in the molecule
Object, such as lead azide (Pb (N3)2), lead styphnate (PbC8HO2(NO2)3) be applied in priming.With boron (B) or silicon
(Si) C or H is replaced, calorific value and density can increase substantially, and scientist attempts to introduce the synthesis of this dvielement in explosive molecules
BN9, TiN9,Zn(C3H9N9) etc., but synthesis condition is harsh, and only theory study is worth.In addition metallic element is generally using complexing
Mode exists, as the double azidos of four ammonia of metal complex explosive perchloric acid close cobalt (III) (1.75g/cm3) and four ammonia pair
(3,5- nitro-triazole) closes copper (1.81g/cm3), since the big steric hindrance of complexing agent limits the density of the molecule containing energy, so that
Global density and CHON explosive are suitable.Metallic element is introduced in the molecule, so that energy density dramatically increases, however stability
Difference, synthesis condition are harsh.
Early period is a large amount of studies have shown that being introduced directly into this molecule of CHOH nonmetallic close with metallic element raising energy
The method of degree is infeasible.In recent years, it in order to which nonmetallic and metallic element is introduced into synthesis in a molecule, improves and contains energy
The energy density of material develops the metal organic framework compound containing energy (Metal Organic Frameworks, MOFs).Gold
Belong to organic frame compound and belong to coordination polymer, be it is a kind of nibbled or nibbled more by two by discrete metal ion or ion cluster match
Body, such as aromatic polycarboxylic acid or polyamine interconnection and self assembly and the crystalline material that is formed, have changeable topology
The regular pore canal of structure and specific dimensions.The preparation method of the metal organic framework compound containing energy is simple, yield is high, by changing
Become the type of metal ion and organic ligand.But it is a large amount of the study found that containing can metal organic framework compound safety pole
Difference, easily heat, power etc. stimulation under explode, lead to not using.
Summary of the invention
In order to overcome the above technical defects, the present invention provides a kind of organic inorganic hybridization energetic material and its preparation sides
Method, by fluorine element as oxidant in the form of organic matter, high activity metal is as fuel, the group by way of organic inorganic hybridization
Energetic material is filled, the uniformity of microstructure and the size distribution of organic oxidizing agent and inorganic metal fuel is controlled, is formed organic
Inorganic hybridization energetic material obtains the energetic material of high-energy density.
In order to reach above-mentioned technical effect, the invention discloses a kind of organic inorganic hybridization energetic material, the material containing energy
Material is by organic oxidizing agent and inorganic metal fuel composition, and wherein organic oxidizing agent is selected from polytetrafluoroethylene (PTFE), fluorinated graphene, perfluor
In carboxylic acid, vinylidene-chlorotrifluoroethylene 1:1 copolymer and vinylidene-chlorotrifluoroethylene 1:4 copolymer any one or
It is several, any one or a few in aluminium, magnesium, boron, silicon and titanium of the inorganic metal fuel.
The present invention also provides a kind of preparation methods of organic inorganic hybridization energetic material, comprising the following steps:
(1) organic oxidizing agent and inorganic metal fuel are selected according to chemical heat release amount；
(2) organic oxidizing agent and inorganic metal fuel are carried out by hydridization assembling using physical-chemical method, obtains group
Point and the uniform organic inorganic hybridization energetic material of structure, wherein organic oxidizing agent and inorganic metal fuel size are distributed in 100
Within nanometer range, including nanometer, sub-nanometer and cluster scale.
Further technical solution is that step (1) is specially the life according to organic oxidizing agent and inorganic metal fuel reaction
Cheng Han calculates energy density, if energy density is greater than HMX (octogen) explosive, that is, the oxidation being chosen as in the present invention
Agent and fuel.
Further technical solution is, the organic oxidizing agent is selected from tetrafluoroethene, fluorinated graphene, perfluorocarboxylic acid, partially
Any one or a few in vinyl fluoride-chlorotrifluoroethylene 1:1 copolymer and vinylidene-chlorotrifluoroethylene 1:4 copolymer.
Further technical solution is that the inorganic metal fuel is selected from one or more of aluminium, magnesium, boron, silicon and titanium.
Further technical solution is that the physical-chemical method includes magnetron sputtering assembling hybrid inorganic-organic containing energy
Material, in-situ chemical reaction synthesis metal fuel assemble organic inorganic hybridization energetic material.
Further technical solution is that the hydridization is assembled under high-purity argon gas or high pure nitrogen protection environment and carries out.
Compared with prior art, the invention has the following beneficial effects: (1) to pass through hybrid structure for organic oxidizing agent and nothing
Machine metal fuel is assembled, and the organic composite of high energy element is realized, for formed high-energy density energetic material design and
Preparation provides a kind of new idea and method.(2) organic oxidizing agent and metal fuel, proportion and group are assembled by the method for hydridization
At adjustable, preparation process and simple process, it is easy to mass preparation.(3) the hybrid inorganic-organic energetic material tool that assembling is formed
There are high energy density and safety.
Specific embodiment
Embodiment 1
Hybrid inorganic-organic energetic material is assembled using magnetically controlled sputter method, by organic oxide PTFE and metal fuel
It is intracavitary that the target of Al is mounted on magnetron sputtering, will vacuumize (2 × 10 in cavity-5Pa), after ready, power supply is opened, is passed through
High-purity Ar (99.9999%) gas, cycle alternation deposit organic matter and metal fuel, the stoichiometric ratio of organic matter and inorganic metal
It is controlled by the time, assembling obtains PTFE the and Al energetic material of organic inorganic hybridization, and the energy density of the energetic material can be with
Reach 20KJ/cm3。
Embodiment 2
Hybrid inorganic-organic energetic material is assembled using magnetically controlled sputter method, by organic oxide PTFE and metal fuel
It is intracavitary that the target of Mg is mounted on magnetron sputtering, will vacuumize (2 × 10 in cavity-5Pa), after ready, power supply is opened, is passed through
High-purity Ar (99.9999%) gas, cycle alternation deposit organic matter and metal fuel, the stoichiometric ratio of organic matter and inorganic metal
It is controlled by the time, assembling obtains PTFE the and Mg energetic material of organic inorganic hybridization, and the energy density of the energetic material can be with
Reach 13.2KJ/cm3。
Embodiment 3
Hybrid inorganic-organic energetic material is assembled using magnetically controlled sputter method, by organic oxide PTFE and metal fuel
It is intracavitary that the target of Ti is mounted on magnetron sputtering, will vacuumize (2 × 10 in cavity-5Pa), after ready, power supply is opened, is passed through
High-purity Ar (99.9999%) gas, cycle alternation deposit organic matter and metal fuel, the stoichiometric ratio of organic matter and inorganic metal
It is controlled by the time, assembling obtains PTFE the and Ti energetic material of organic inorganic hybridization, and the energy density of the energetic material can be with
Reach 8.3KJ/cm3。
Embodiment 4
Hybrid inorganic-organic energetic material is assembled using magnetically controlled sputter method, organic oxide (PTFE) and metal are fired
It is intracavitary that the target of material (B) is mounted on magnetron sputtering, will vacuumize (2 × 10 in cavity-5Pa), after ready, power supply is opened, is led to
Enter high-purity Ar (99.9999%) gas, cycle alternation deposits organic matter and metal fuel, the stoichiometry of organic matter and inorganic metal
Than being controlled by the time, assembling obtains PTFE the and B energetic material of organic inorganic hybridization, and the energy density of the energetic material can be with
Reach 6.9KJ/cm3。
Embodiment 5
In a solvent by organic fluorine oxidiser (fluorinated graphene) dispersion, by organic reagent (H3Al·NMe3) be added to and contain
Have in the solution of fluorinated graphene, adds isopropyl titanate Ti (O-i-Pr)4, H is made by electronation3Al·NMe3Reaction
Aluminium atom is produced in fluorinated graphene surface in situ, forms aluminium cluster, immediately in fluorinated graphene surface-assembled, forms molecular group
The Organic fluoride of dress/aluminium hydridization energetic material, is centrifugated after the reaction was completed, and dehydrated alcohol washing, experimentation is in glove box
Or carried out under high pure nitrogen protection environment, the energy density of the energetic material can achieve 13.5KJ/cm3。
Embodiment 6
Organic fluorine oxidiser (perfluorocarboxylic acid) is dispersed in ether solvent, by organic reagent (H3Al·NMe3) be added to
In solution containing perfluorocarboxylic acid, isopropyl titanate Ti (O-i-Pr) is added4, H is made by electronation3Al·NMe3Reaction
Aluminium cluster is formed, is assembled immediately with perfluorocarboxylic acid, Organic fluoride/aluminium hydridization energetic material of molecule assembling, reaction are formed
It is centrifugated after the completion, dehydrated alcohol washing, experimentation carries out under glove box or high pure nitrogen protection environment, this contains energy
The energy density of material can achieve 15.3KJ/cm3。
Embodiment 7
Organic fluorine oxidiser (F2311) is dispersed in ethyl acetate solvent, by organic reagent (H3Al·NMe3) be added to
In solution containing F2311, isopropyl titanate Ti (O-i-Pr) is added4, H is made by electronation3Al·NMe3Reaction is formed
Aluminium cluster, is assembled with F2311 immediately, formed molecule assembling Organic fluoride/aluminium hydridization energetic material, after the reaction was completed from
Heart separation, dehydrated alcohol washing, experimentation carry out under glove box or high pure nitrogen protection environment, the energy of the energetic material
Metric density can achieve 12.1KJ/cm3。
Embodiment 8
By organic reagent (H3Al·NMe3) be dissolved in diethyl etherate, it adds it in the solution containing F2314.
Add isopropyl titanate Ti (O-i-Pr)4, H is made by electronation3Al·NMe3Reaction forms aluminium cluster, with F2314 group
Dress forms Organic fluoride/aluminium hydridization energetic material, is centrifugated after the reaction was completed, dehydrated alcohol washing.Experimentation is in gloves
It is carried out under case or high pure nitrogen protection environment, the energy density of the energetic material can achieve 11.9KJ/cm3。
Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair
Bright preferable embodiment, embodiment of the present invention are not limited by the above embodiments, it should be appreciated that those skilled in the art
Member can be designed that a lot of other modification and implementations, these modifications and implementations will fall in principle disclosed in the present application
Within scope and spirit.
Claims (7)
1. a kind of organic inorganic hybridization energetic material, which is characterized in that the energetic material is by organic oxidizing agent and inorganic metal
Fuel composition, wherein organic oxidizing agent is selected from polytetrafluoroethylene (PTFE), fluorinated graphene, perfluorocarboxylic acid, vinylidene-chlorotrifluoroethylene
Any one or a few in 1:1 copolymer and vinylidene-chlorotrifluoroethylene 1:4 copolymer, the inorganic metal fuel choosing
From any one or a few in aluminium, magnesium, boron, silicon and titanium.
2. a kind of preparation method of organic inorganic hybridization energetic material, which comprises the following steps:
(1) organic oxidizing agent and inorganic metal fuel are selected according to chemical heat release amount；
(2) organic oxidizing agent and inorganic metal fuel are carried out by hydridization assembling using physical-chemical method, obtain component and
The uniform organic inorganic hybridization energetic material of structure, wherein the size of organic oxidizing agent and inorganic metal fuel is distributed in 100 and receives
Within rice range, including nanometer, sub-nanometer and cluster size.
3. the preparation method of organic inorganic hybridization energetic material according to claim 2, which is characterized in that the step
(1) energy density is specially calculated, if energy density according to the enthalpy of formation of organic oxidizing agent and inorganic metal fuel reaction
Greater than octogen explosive, that is, the oxidant and fuel that are chosen as in the present invention.
4. the preparation method of organic inorganic hybridization energetic material according to claim 2, which is characterized in that the organic oxygen
Agent is selected from tetrafluoroethene, fluorinated graphene, perfluorocarboxylic acid, vinylidene-chlorotrifluoroethylene 1:1 copolymer and vinylidene-
Any one or a few in chlorotrifluoroethylene 1:4 copolymer.
5. the preparation method of organic inorganic hybridization energetic material according to claim 2, which is characterized in that the inorganic gold
Belong to fuel and is selected from one or more of aluminium, magnesium, boron, silicon and titanium.
6. the preparation method of organic inorganic hybridization energetic material according to claim 2, which is characterized in that the physics-
Chemical method includes that magnetron sputtering assembles hybrid inorganic-organic energetic material, in-situ chemical reaction synthesis metal fuel is assembled with
Machine inorganic hybridization energetic material.
7. the preparation method of organic inorganic hybridization energetic material according to claim 2, which is characterized in that the hydridization group
Dress process carries out under high-purity argon gas or high pure nitrogen protection environment.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110903153A (en) * | 2019-12-17 | 2020-03-24 | 宜昌市恒益亚盛科技有限责任公司 | High plasticity energetic structure |
| CN114890855A (en) * | 2022-04-24 | 2022-08-12 | 江苏理工学院 | Interlayer hybrid energy-containing structural material and preparation method thereof |
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| US5472533A (en) * | 1994-09-22 | 1995-12-05 | Alliant Techsystems Inc. | Spectrally balanced infrared flare pyrotechnic composition |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903153A (en) * | 2019-12-17 | 2020-03-24 | 宜昌市恒益亚盛科技有限责任公司 | High plasticity energetic structure |
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| CN114890855A (en) * | 2022-04-24 | 2022-08-12 | 江苏理工学院 | Interlayer hybrid energy-containing structural material and preparation method thereof |
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Application publication date: 20190405 |