CN107353175A - A kind of preparation method of CL 20/GAP Nanocomposite Energetic Materials - Google Patents
A kind of preparation method of CL 20/GAP Nanocomposite Energetic Materials Download PDFInfo
- Publication number
- CN107353175A CN107353175A CN201610535262.7A CN201610535262A CN107353175A CN 107353175 A CN107353175 A CN 107353175A CN 201610535262 A CN201610535262 A CN 201610535262A CN 107353175 A CN107353175 A CN 107353175A
- Authority
- CN
- China
- Prior art keywords
- gap
- preparation
- energetic materials
- nanocomposite energetic
- nanocomposite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
- C06B25/40—Compositions containing a nitrated organic compound the compound being a nitroparaffin with two or more nitroparaffins present
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Preparation (AREA)
Abstract
A kind of preparation method of CL 20/GAP Nanocomposite Energetic Materials, CL 20, GAP are dissolved in solvent, are configured to clear solution, and surfactant mixed liquor is added dropwise, and configured good solution is carried out into vacuum freeze drying after stirring.The sample of vacuum freeze drying will be completed, centrifugal sedimentation after being washed successively with water, ethanol, obtained solid is dried, that is, obtains CL 20/GAP Nanocomposite Energetic Materials.Preparation method of the invention is workable, required equipment is simple, prepared composite good dispersion, security performance are high, and oxidant and fuel ratio, particle size and size distribution are controllable, thinking is provided for the development of following energetic material, existing dangerous complicated energetic material manufacture craft may completely or partially be substituted, be the important directions of the Energetic Nanomaterials such as solid propellant and explosive wastewater technology development.
Description
Technical field
The present invention relates to a kind of composite-Hexanitrohexaazaisowurtzitane（Hereinafter referred to as CL-20）/ glycidol
Azide polyethers（Hereinafter referred to as GAP）The preparation method of base Nanocomposite Energetic Materials.
Background technology
Nanocomposite Energetic Materials not only have all properties of common energetic material, also with new superiority, if
Improve crystal morphology, reduce sensitivity, improve mechanical property, the rate of release of energy, the conversion ratio of burning and the nanometer of gunpowder
Free-running property of particle etc., can make the release of explosion energy more completely, detonation is closer to perfect condition.In the related neck of national defence
Domain, the application of Nanocomposite Energetic Materials are expected to improve conventional explosives, propellant, pyrotechnics within one period in the recent period or from now on
Stability, energy output and the mechanical property of agent.
Nanocomposite Energetic Materials are made up of the matrix and the energy-containing compound of organic or inorganic to play a supportive role, wherein
The specification that at least one component defines in nanometer（Usual 1-100nm）It is interior.It can wherein be aoxidized as the material of skeleton including metal
Thing（Such as Fe2O3、Al2O3、CuO、Mo2O3Deng）, silica, phenolic resin（RF）Deng, but these are inert components, its energy
It is low, it is difficult to meet the requirement for further improving energy.Therefore when preparing Nanocomposite Energetic Materials, if with nitrocotton（NC）、
Glycidol azide polyethers（GAP）It is that skeleton can further improve maximum system energy Deng energetic material.As GAP side chain in one
Azido group can just provide about 314 ~ 398kJ positive generation heat, and its combustion product relative molecular mass is low, does not produce cigarette
Mist, not only improves and improves energy and burn rate, and and can reduces flame temperature and smoke signal.
Existing literature report prepares it is this have containing can matrix type Nanocomposite Energetic Materials method mostly be colloidal sol-
Gel method, will contain the compound of high chemical active ingredient by solution, colloidal sol, gel and solidify, then removed through different methods
Solvent is removed so as to obtain Composite Energetic Materials.Such as Bryce CT（Propellants, Explos, Pyrotech, 2006,31）
With nitrocotton（NC）, glycidyl azide polymer（GAP）For gel skeleton, by sol-gel process be prepared for CL-20/GAP,
The Nanocomposite Energetic Materials such as CL-20/NC；Jin Miaomiao etc.（War industry's journal, 2014,35）Prepared using sol-gel process
The RDX/NC Nanocomposite Energetic Materials of different RDX contents.The shortcomings that sol-gel process be in the drying process, it is molten in gel
Pressure caused by the evaporation of agent can cause gel pore contraction to collapse, and nano particle is easily reunited and is grown up, lose a nanometer material
Due characteristic is expected, so as to hinder the application for preparing product.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of preparation CL-20/GAP simple to operate, safe and received
The method of rice Composite Energetic Materials.
The technical solution of the present invention comprises the following steps：
（1）CL-20, GAP are dissolved in a small amount of solvent, are configured to clear solution；
（2）Ready surfactant mixed liquor is added dropwise in above-mentioned solution, stirs；
（3）Configured good solution is subjected to vacuum freeze drying；
（4）The sample for completing vacuum freeze drying is taken out, water washing is added, solid is obtained by centrifuge, by the solid again
Centrifugal sedimentation after being washed with ethanol.
（5）Obtained solid is dried, that is, obtains CL-20/GAP Nanocomposite Energetic Materials.
The step（1）Solvent be isobutyl acetate, the combination of one or both of ethyl acetate.
The step（1）CL-20 concentration is 30 ~ 45 g/L in the solution of middle configuration, and GAP concentration is 5~20 g/L.
The step（2）In the volume of surfactant mixed liquor be step（1）10 ~ 12 times of middle quantity of solvent.
The step（2）In surfactant mixed liquor containing the % of 70 % ~ 75（Percentage by weight, similarly hereinafter）The % of water, 5 % ~ 8
Lauryl sodium sulfate（SDS）, the % n-butanols of 17 % ~ 25.
The step（2）In surfactant mixed liquor be added dropwise speed be 30 ~ 120 drops/min.
The step（2）In stir speed (S.S.) be 200 ~ 400 rmp/min, mixing time is the h of 2 h ~ 6.
The step（1）~（2）Carry out at room temperature.
The step（3）Middle cryogenic temperature is -25 DEG C ~ -45 DEG C, vacuum ＜ 1mbar.
The step（4）The water of middle addition is deionized water, and washing times is three times.
The step（4）The rotating speed of middle centrifuge work be 5000 ~ 20000 rpm/min, and the time is the min of 2 min ~ 5.
The step（5）45 DEG C~65 DEG C of drying temperature, drying time is the h of 2 h~48.
The present invention contains a kind of Hexanitrohexaazaisowurtzitane（CL-20）/ glycidol azide polyethers（GAP）Ji Na
The preparation method of rice Composite Energetic Materials, i.e. two kinds of immiscible continuous medias are divided into short space shape by surfactant
Into microreactor, its size can be controlled in nano-scale range.The advantage of the invention is that：First, contain energy in composite
Component can realize nanosizing, can accurately control oxidant constituents and the ratio of fuel element in composite, particle diameter and steady
It is qualitative, you can by adjusting the volume of microemulsion droplets reclaimed water and the concentration of various reactants so as to obtaining the nanometer of various particle diameters
Composite Energetic Materials；Secondly reaction is all in small diameter of Spherical Volume, the surfactant of particle surface can be avoided effectively
Intergranular reunion, therefore obtained nano particle diameter is small, form is regular, monodispersity is good and is mostly spherical or class ball
Shape.Thirdly the experimental provision and operation needed for the method are simpler, condition is easily achieved.
The present invention is improving the component Special safety containing energy using microemulsion method preparation matrix type Nanocomposite Energetic Materials containing energy
Property, energy releasing efficiency and mechanical property etc. have good prospect, can be applied to solid propellant, explosive wastewater and pyrotechnics
The fields such as medicine.The inventive method can be controlled to the particle diameter and stability of nano material, and the nanometer that various particle diameters are made contains
Can particle.The existing document report on microemulsion method is to be used to prepare the ultra-fine energy-containing compound of simple substance, there is not yet for making
The report of the standby matrix type Nanocomposite Energetic Materials containing energy.
In a word, preparation method provided by the invention is workable, required equipment is simple, and prepared composite disperses
Property it is good, security performance is high, and oxidant and fuel ratio, particle size and size distribution are controllable, develop for following energetic material
Provide thinking, may completely or partially substitute existing dangerous complicated energetic material manufacture craft, be solid propellant and
The important directions of the Energetic Nanomaterials such as explosive wastewater technology development.
Embodiment
Embodiment 1
At room temperature, 9 g CL-20,1 g GAP are dissolved in 200 ml isobutyl acetates, are configured to clear solution, with 30 drop/
Ready 2 L water, 200 g SDS, 500 ml n-butanol mixed liquors, 200 rmp/min rotating speed stirring is added dropwise in min speed
After 2 h, configured good solution is subjected to the h of vacuum freeze drying 18（- 25 DEG C, the mbar of ＜ 1）.Take out and complete vacuum refrigeration
Dry sample, add deionized water washing three times, pass through centrifuge（Rotating speed is 5000 rpm/min, and the time is 2 min）
To solid, centrifugal sedimentation after the solid is washed with ethanol again.By obtained solid in 45 DEG C of dry 2 h, that is, obtain CL-
20/GAP Nanocomposite Energetic Materials.
Embodiment 2
At room temperature, 8 g CL-20,2 g GAP are dissolved in 200 ml ethyl acetates, are configured to clear solution, with 60 drop/
Ready 1.9 L water, 135 g SDS, 460 ml n-butanol mixed liquors are added dropwise in min speed, and 400 rmp/min rotating speed stirs
After mixing 3 h, configured good solution is subjected to the h of vacuum freeze drying 24（- 30 DEG C, the mbar of ＜ 1）.It is cold to take out completion vacuum
Lyophilized dry sample, add deionized water washing three times, pass through centrifuge（Rotating speed is 10000 rpm/min, and the time is 3 min）
Solid is obtained, centrifugal sedimentation after the solid is washed with ethanol again.By obtained solid in 50 DEG C of dry 24 h, that is, obtain
CL-20/GAP Nanocomposite Energetic Materials.
Embodiment 3
At room temperature, 7 g CL-20,3 g GAP are dissolved in 200 ml isobutyl acetates, clear solution are configured to, with 80
Ready 2 L water, 216 g SDS, 675 ml n-butanol mixed liquors, 300 rmp/min rotating speed is added dropwise in drop/min speed
After stirring 4 h, configured good solution is subjected to the h of vacuum freeze drying 30（- 35 DEG C, the mbar of ＜ 1）.Take out and complete vacuum
The sample of freeze-drying, add deionized water washing three times, pass through centrifuge（Rotating speed is 15000 rpm/min, the time 4
min）Solid is obtained, centrifugal sedimentation after the solid is washed with ethanol again.By obtained solid in 55 DEG C of dry 48 h, i.e.,
Obtain CL-20/GAP Nanocomposite Energetic Materials.
Embodiment 4
At room temperature, 6 g CL-20,4 g GAP are dissolved in 200 ml ethyl acetates, are configured to clear solution, with 100 drop/
Ready 2 L water, 180 g SDS, 550 ml n-butanol mixed liquors, 250 rmp/min rotating speed stirring is added dropwise in min speed
After 2.5 h, configured good solution is subjected to the h of vacuum freeze drying 18（- 40 DEG C, the mbar of ＜ 1）.It is cold to take out completion vacuum
Lyophilized dry sample, add deionized water washing three times, pass through centrifuge（Rotating speed is 20000 rpm/min, and the time is 5 min）
Solid is obtained, centrifugal sedimentation after the solid is washed with ethanol again.By obtained solid in 60 DEG C of dry 12 h, that is, obtain
CL-20/GAP Nanocomposite Energetic Materials.
Embodiment 5
At room temperature, 90 g CL-20,10 g GAP are dissolved in 2000 ml isobutyl acetates, are configured to clear solution, with
Ready 19 L water, 1650 g SDS, 5000 ml n-butanol mixed liquors, 350 rmp/min are added dropwise in 120 drops/min speed
Rotating speed stir 3.5 h after, configured good solution is subjected to the h of vacuum freeze drying 24（- 45 DEG C, ＜ 1mbar）.Take out
Into the sample of vacuum freeze drying, add deionized water washing three times, pass through centrifuge（Rotating speed is 15000 rpm/min, the time
For 5 min）Solid is obtained, centrifugal sedimentation after the solid is washed with ethanol again.Obtained solid is dried 48 at 65 DEG C
H, that is, obtain CL-20/GAP Nanocomposite Energetic Materials.
Claims (10)
1. a kind of preparation method of CL-20/GAP Nanocomposite Energetic Materials, it is characterised in that comprise the following steps：
（1）CL-20, GAP are dissolved in solvent, are configured to clear solution；
（2）Surfactant mixed liquor is added dropwise in above-mentioned solution, stirs；
（3）Configured good solution is subjected to vacuum freeze drying；
（4）The sample for completing vacuum freeze drying is taken out, deionized water is added and removes unnecessary surfactant, pass through centrifuge
Solid is obtained, centrifugal sedimentation after the solid is washed with ethanol again；
（5）Obtained solid is dried, that is, obtains CL-20/GAP Nanocomposite Energetic Materials.
2. the preparation method of CL-20/GAP Nanocomposite Energetic Materials according to claim 1, it is characterised in that：The step
Suddenly（1）Solvent be isobutyl acetate, the combination of one or both of ethyl acetate.
3. the preparation method of CL-20/GAP Nanocomposite Energetic Materials according to claim 1, it is characterised in that：The step
Suddenly（1）CL-20 concentration is 30 ~ 45 g/L in the solution of middle configuration, and GAP concentration is 5~20 g/L.
4. the preparation method of CL-20/GAP Nanocomposite Energetic Materials according to claim 1, it is characterised in that：The step
Suddenly（2）In the volume of surfactant mixed liquor be step（1）10 ~ 12 times of middle quantity of solvent.
5. the preparation method of CL-20/GAP Nanocomposite Energetic Materials according to claim 1, it is characterised in that：The step
Suddenly（2）In surfactant mixed liquor containing the % water of 70 % ~ 75, the % lauryl sodium sulfate of 5 % ~ 8, the % n-butanols of 17 % ~ 25,
It is above-mentioned to be weight percentage.
6. the preparation method of CL-20/GAP Nanocomposite Energetic Materials according to claim 1, it is characterised in that：The step
Suddenly（2）In surfactant mixed liquor be added dropwise speed be 30 ~ 120 drops/min.
7. the preparation method of CL-20/GAP Nanocomposite Energetic Materials according to claim 1, it is characterised in that：The step
Suddenly（2）In stir speed (S.S.) be 200 ~ 400 rmp/min, mixing time is the h of 2 h ~ 6.
8. the preparation method according to claim 1 for preparing CL-20/GAP Nanocomposite Energetic Materials, it is characterised in that：
The step（3）Middle cryogenic temperature is -25 ~ -45 DEG C, the mbar of vacuum ＜ 1.
9. the preparation method according to claim 1 for preparing CL-20/GAP Nanocomposite Energetic Materials, it is characterised in that：
The step（4）The rotating speed of middle centrifuge work be 5000 ~ 20000 rpm/min, and the time is the min of 2 min ~ 5.
10. the preparation method of CL-20/GAP Nanocomposite Energetic Materials according to claim 1, it is characterised in that：The step
Suddenly（5）45 DEG C~65 DEG C of drying temperature, drying time is the h of 2 h~48.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610535262.7A CN107353175A (en) | 2016-07-08 | 2016-07-08 | A kind of preparation method of CL 20/GAP Nanocomposite Energetic Materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610535262.7A CN107353175A (en) | 2016-07-08 | 2016-07-08 | A kind of preparation method of CL 20/GAP Nanocomposite Energetic Materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107353175A true CN107353175A (en) | 2017-11-17 |
Family
ID=60271447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610535262.7A Pending CN107353175A (en) | 2016-07-08 | 2016-07-08 | A kind of preparation method of CL 20/GAP Nanocomposite Energetic Materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107353175A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079676A (en) * | 2020-08-06 | 2020-12-15 | 北京理工大学 | Composite energetic material with micro-nano layered structure and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198681A (en) * | 2014-06-10 | 2015-12-30 | 湖北航天化学技术研究所 | Room-temperature-cured-type clean solid propellant |
| CN105481617A (en) * | 2016-01-06 | 2016-04-13 | 中北大学 | Nano-composite energetic material and preparation method thereof |
-
2016
- 2016-07-08 CN CN201610535262.7A patent/CN107353175A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198681A (en) * | 2014-06-10 | 2015-12-30 | 湖北航天化学技术研究所 | Room-temperature-cured-type clean solid propellant |
| CN105481617A (en) * | 2016-01-06 | 2016-04-13 | 中北大学 | Nano-composite energetic material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| LI,J: "Nanostructured energetic composites of CL-20 and binders synthesized by sol gel methods", 《PROPELLANTS EXPLOSIVES PYROTECHNICS》 * |
| 张娟: "RDX/RF纳米复合含能微球的乳液溶胶-凝胶制备", 《含能材料》 * |
| 陈星: "溶胶凝胶法制备纳米复合含能材料的研究", 《万方数据知识服务平台》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079676A (en) * | 2020-08-06 | 2020-12-15 | 北京理工大学 | Composite energetic material with micro-nano layered structure and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Qiu et al. | RDX-based nanocomposite microparticles for significantly reduced shock sensitivity | |
| He et al. | Highly reactive metastable intermixed composites (MICs): preparation and characterization | |
| US6454886B1 (en) | Composition and method for preparing oxidizer matrix containing dispersed metal particles | |
| CN103201027B (en) | By the preparation of emulsion and the method for Explosive detonation nano material and products thereof and emulsion | |
| Han et al. | Fabrication of microspherical Hexanitrostilbene (HNS) with droplet microfluidic technology | |
| CN101844954A (en) | Microporous smokeless firework explosive and preparation method thereof | |
| WO2001038265A1 (en) | Variable burn-rate propellant | |
| Ma et al. | Preparation and characterization of ultra-fine ammonium perchlorate crystals using a microfluidic system combined with ultrasonication | |
| Jia et al. | Synthesis, thermolysis, and solid spherical of RDX/PMMA energetic composite materials | |
| Pang et al. | Effect of nano-sized energetic materials (nEMs) on the performance of solid propellants: A review | |
| Bian et al. | Preparation and characterization of cellulose/RDX composite aerogel spheres | |
| CN105253857A (en) | Method for preparing micro-ammonium perchlorate | |
| Tian et al. | Anti‐hygroscopicity technologies for ammonium dinitramide: A review | |
| CN106220460A (en) | A kind of preparation method of graphene-based Composite Energetic Materials | |
| Liu et al. | Crystal phase control and ignition properties of HNS/CL-20 composite microspheres prepared by microfluidics combined with emulsification techniques | |
| US8936689B1 (en) | Insensitive explosives and process therefore | |
| CN107353175A (en) | A kind of preparation method of CL 20/GAP Nanocomposite Energetic Materials | |
| Hou et al. | Efficient Preparation and Performance Characterization of the HMX/F2602 Microspheres by One‐Step Granulation Process | |
| CN103201212B (en) | By emulsifying while emulsion and the method for detonation continuous synthesis nano material | |
| CN108976176A (en) | 3,3 '-diamino -4, the thinning method of 4 '-azoxy furazan explosive crystals | |
| CN106518883B (en) | Six azepine isoamyl of nanometer ε crystal form hexanitro hereby alkane explosive and its batch preparation | |
| CN105367362B (en) | New peak reaction enthalpy energetic material and preparation method thereof | |
| CN101844955B (en) | Method for sensitizing microporous smokeless firework explosive | |
| CN107473911A (en) | Method based on emulsion method regulation energetic material oxygen balance | |
| Li et al. | The preparation and properties of AP-based nano-limit growth energetic materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171117 |