CN106748593A - A kind of UV photocurings based on micro/nano level CL 20 ink containing energy and preparation method thereof - Google Patents
A kind of UV photocurings based on micro/nano level CL 20 ink containing energy and preparation method thereof Download PDFInfo
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- CN106748593A CN106748593A CN201611215652.2A CN201611215652A CN106748593A CN 106748593 A CN106748593 A CN 106748593A CN 201611215652 A CN201611215652 A CN 201611215652A CN 106748593 A CN106748593 A CN 106748593A
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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
- C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/009—Wetting agents, hydrophobing agents, dehydrating agents, antistatic additives, viscosity improvers, antiagglomerating agents, grinding agents and other additives for working up
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a kind of UV photocurings based on micro/nano level CL 20 ink containing energy, the ink includes following components：Nitrocotton, acetone, styrene, binder, aromatic solvent, micro/nano level CL 20, UV light curing agents.The ink solids are high, and viscosity and rheological characteristic with appropriateness, are very suitable for being applied in direct writing technology, and solid is well dispersed, are not in a stifled phenomenon, performance safety, stabilization in direct write deposition.
Description
Technical field
The present invention relates to explosive field, more particularly to a kind of UV photocurings based on micro/nano level CL-20 ink containing energy
And preparation method thereof.
Background technology
CL-20, scientific name is Hexanitrohexaazaisowurtzitane, is a kind of more prominent single chmical compound explosive of combination property.CL-
20 is many ammonium nitrate compounds of a kind of high-energy-density cage modle that Recent study goes out, and wherein element composition includes 16.44% C,
1.36% H, 38.35% N, 43.81% O.There are four kinds of crystal formations in CL-20, be current density and energy at normal temperatures and pressures
One of horizontal highest single chmical compound explosive is measured, is military quick-fried high explosive high, be that the high-lighting of third generation explosive is represented.
The deposition direct writing technology of the ink containing energy is similar with the principle of injection molding technology, is by means of the side such as air pressure, hydraulic pressure
Formula to containing can ink apply pressure, to extrude injection in the way of by storage room containing can ink squeeze out micro- nib, control
Energy ink direct write deposition will be contained under the control of system processed on substrate, set by techniques such as heat treatment or photocurings afterwards
Count the energetic material deposition of figure.
The ink direct writing technology containing energy is that advanced direct-write process is combined so as to solve the micro- chi of priming system with pyrotechnics technique
Spend the problem of powder charge.Direct writing technology has significant development in recent years, and the scope for using is also more and more wider.The ink containing energy is main by containing
Energy material, binding agent, solvent and additive composition, in suspension or collosol state.Energetic material is typically in the ink containing energy
It is scattered in ink with particulate form so that the viscosity of ink is larger, while energetic material has to be heated easily decompose, high temperature easy firing
The characteristics of blast, therefore it is required that direct-write process must be adapted for viscosity suspension high and can not enter in high temperature environments
OK.At present, can be used for the direct writing technology containing energy ink mainly has microfluidic to deposit and micro- spray snake deposition direct writing technology.Wherein
Solid content is relatively low, viscosity is relatively low containing can ink can be used for micro-injection deposition direct write, and solid content is higher, viscosity is higher contains
Energy ink is then adapted to microfluidic deposition direct writing technology.On the whole, direct writing technology to containing can the solid content of ink, mechanical strength,
Line width, cruelly Hong critical dimension and sensitivity etc. have requirement higher.
The content of the invention
It is an object of the invention to provide a kind of UV photocurings based on micro/nano level CL-20 ink containing energy, the ink contains admittedly
Amount is high, and viscosity and rheological characteristic with appropriateness, is very suitable for being applied in direct writing technology, and solid is well dispersed,
Be not in a stifled phenomenon, performance safety, stabilization during direct write deposition.
It is a further object of the present invention to provide preparation side of the UV photocurings containing energy ink that this is based on micro/nano level CL-20
Method.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of UV photocurings based on micro/nano level CL-20 containing energy ink, comprises the following steps：
(1) 100 parts of CL-20 and 100-150 parts of ultra-pure waters are added in ball grinder, and are added thereto to 700-900 parts
Zirconium oxide ball milling pearl, is ground with the speed of 140-160rpm, every 30min switching-over grindings direction, persistently grinds 10-16h, afterwards
After the CL-20 suction filtrations after grinding, freeze-drying under vacuum condition obtains final product micro/nano level CL-20 particles；
(2) dry nitrocotton 1-2 parts is dissolved in 3-4 parts of acetone, is stirred, 4-6 is added thereto to afterwards
Part styrene, 0.5-0.9 parts of binder, 10-13 parts of aromatic solvent, are stirred with the speed of 40-60rpm, and are turned per 5min
Mixing direction is changed, after stirring 20min, 40-60 parts of obtained micro/nano level CL-20 particles in previous step is added thereto to, after
After continuous stirring 30-45min, 3-5 parts of UV light curing agent is added, after continuing to stir 10-15min, obtain final product the UV photocurings containing energy
Ink.
Preferably, the zirconium oxide ball milling pearl for diameter 3mm and diameter 1mm etc. mass mixing thing.
Preferably, the particle diameter of the micro/nano level CL-20 particles is 600-1200nm.
Preferably, the binder is one or more in HTPB, poly epihydric alcohol nitrate or epoxy acrylate
Mixture.
Preferably, the aromatic solvent is benzene, toluene or dimethylbenzene.
Preferably, the UV light curing agents are Isosorbide-5-Nitrae-hydroxymethyl-cyclohexane, 2,4,6- trimethylbenzoyl dipheny oxides
Change the mixture of phosphorus and N- vinylpyrrolidones.
A kind of UV photocurings based on micro/nano level CL-20 ink containing energy, is prepared from by the above method.
Wherein aromatic solvent is for that can dissolve binder but can not dissolve CL-20, and the virtue that will not be reacted with CL-20
Fragrant race's solvent.
The invention has the advantages that, micro-nano CL-20 is used for the material containing energy, will by planet abrading-ball polishing
CL-20 particles of the grinding as micro/nano level, is more beneficial for it and is scattered in ink, and preparation method is simple.This contains can ink
Water is not in stifled when direct write deposition is carried out with suitable viscosity and rheological characteristic on the premise of ensureing that solid content is higher
The phenomenon of pen or separation of solid and liquid, stable performance.Additionally, the ink is after UV light irradiation solidifications are carried out, the burning that can stablize,
Detonation critical dimension is small.Sum it up, the ink is prepared simply, combination property is high, and suitable application area is extensive, with practicality higher
Value.
Specific embodiment
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solution
The present invention is released, any restriction will not be constituted to the present invention.
Embodiment 1
(1) 100 parts of CL-20 and 100 part of ultra-pure waters are added in ball grinder, and are added thereto to 700-900 parts of oxidation
Zirconium ball milling pearl, is ground with the speed of 140rpm, every 30min switching-over grindings direction, 10h is persistently ground, afterwards by after grinding
After CL-20 suction filtrations, freeze-drying under vacuum condition obtains final product micro/nano level CL-20 particles；
(2) by dry nitrocotton 1 part be dissolved in 3 parts of acetone, stir, 4 parts of benzene second are added thereto to afterwards
Alkene, 0.5 part of HTPB, 10 parts of benzene, are stirred with the speed of 40rpm, and mixing direction is changed per 5min, after stirring 20min, Xiang Qi
Obtained 40 parts of micro/nano level CL-20 particles in middle addition previous step, after continuing to stir 30min, add 3 parts of UV photocurings
Agent, after continuing to stir 10min, obtains final product UV photocurings ink containing energy.
Wherein zirconium oxide ball milling pearl for diameter 3mm and diameter 1mm etc. mass mixing thing, micro/nano level CL-20 particles
Particle diameter is 600-1200nm, and UV light curing agents are Isosorbide-5-Nitrae-hydroxymethyl-cyclohexane, the oxidation of 2,4,6- trimethylbenzoyl diphenyl
The mixture of phosphorus and N- vinylpyrrolidones.
Embodiment 2
(1) 100 parts of CL-20 and 150 part of ultra-pure waters are added in ball grinder, and are added thereto to 900 parts of zirconia balls
Mill pearl, is ground with the speed of 160rpm, every 30min switching-over grindings direction, 16h is persistently ground, afterwards by the CL-20 after grinding
After suction filtration, freeze-drying under vacuum condition obtains final product micro/nano level CL-20 particles；
(2) by dry nitrocotton 2 parts be dissolved in 4 parts of acetone, stir, 6 parts of benzene second are added thereto to afterwards
Alkene, 0.9 part of poly epihydric alcohol nitrate, 13 parts of toluene, are stirred with the speed of 60rpm, and mixing direction is changed per 5min, are stirred
After mixing 20min, obtained 60 parts of micro/nano level CL-20 particles in previous step are added thereto to, after continuing to stir 45min, plus
Enter 5 parts of UV light curing agents, after continuing to stir 15min, obtain final product UV photocurings ink containing energy.
Wherein zirconium oxide ball milling pearl for diameter 3mm and diameter 1mm etc. mass mixing thing, micro/nano level CL-20 particles
Particle diameter is 600-1200nm, and UV light curing agents are Isosorbide-5-Nitrae-hydroxymethyl-cyclohexane, the oxidation of 2,4,6- trimethylbenzoyl diphenyl
The mixture of phosphorus and N- vinylpyrrolidones.
Embodiment 3
(1) 100 parts of CL-20 and 100 part of ultra-pure waters are added in ball grinder, and are added thereto to 900 parts of zirconia balls
Mill pearl, is ground with the speed of 140rpm, every 30min switching-over grindings direction, 16h is persistently ground, afterwards by the CL-20 after grinding
After suction filtration, freeze-drying under vacuum condition obtains final product micro/nano level CL-20 particles；
(2) by dry nitrocotton 1 part be dissolved in 4 parts of acetone, stir, 4 parts of benzene second are added thereto to afterwards
Alkene, 0.9 part of epoxy acrylate, 10 parts of dimethylbenzene, are stirred with the speed of 60rpm, and mixing direction, stirring are changed per 5min
After 20min, obtained 40 parts of micro/nano level CL-20 particles in previous step are added thereto to, after continuing to stir 45min, add 3
Part UV light curing agents, after continuing to stir 15min, obtain final product UV photocurings ink containing energy.
Wherein zirconium oxide ball milling pearl for diameter 3mm and diameter 1mm etc. mass mixing thing, micro/nano level CL-20 particles
Particle diameter is 600-1200nm, and UV light curing agents are Isosorbide-5-Nitrae-hydroxymethyl-cyclohexane, the oxidation of 2,4,6- trimethylbenzoyl diphenyl
The mixture of phosphorus and N- vinylpyrrolidones.
Embodiment 4
(1) 100 parts of CL-20 and 150 part of ultra-pure waters are added in ball grinder, and are added thereto to 700 parts of zirconia balls
Mill pearl, is ground with the speed of 160rpm, every 30min switching-over grindings direction, 10h is persistently ground, afterwards by the CL-20 after grinding
After suction filtration, freeze-drying under vacuum condition obtains final product micro/nano level CL-20 particles；
(2) by dry nitrocotton 2 parts be dissolved in 3 parts of acetone, stir, 6 parts of benzene second are added thereto to afterwards
Alkene, 0.5 part of epoxy acrylate, 13 parts of benzene, are stirred with the speed of 40rpm, and mixing direction, stirring are changed per 5min
After 20min, obtained 60 parts of micro/nano level CL-20 particles in previous step are added thereto to, after continuing to stir 30min, add 5
Part UV light curing agents, after continuing to stir 10min, obtain final product UV photocurings ink containing energy.
Wherein zirconium oxide ball milling pearl for diameter 3mm and diameter 1mm etc. mass mixing thing, micro/nano level CL-20 particles
Particle diameter is 600-1200nm, and UV light curing agents are Isosorbide-5-Nitrae-hydroxymethyl-cyclohexane, the oxidation of 2,4,6- trimethylbenzoyl diphenyl
The mixture of phosphorus and N- vinylpyrrolidones.
Embodiment 5
(1) 100 parts of CL-20 and 120 part of ultra-pure waters are added in ball grinder, and are added thereto to 800 parts of zirconia balls
Mill pearl, is ground with the speed of 150rpm, every 30min switching-over grindings direction, 12h is persistently ground, afterwards by the CL-20 after grinding
After suction filtration, freeze-drying under vacuum condition obtains final product micro/nano level CL-20 particles；
(2) by dry nitrocotton 2 parts be dissolved in 3.5 parts of acetone, stir, 5 parts of benzene are added thereto to afterwards
Ethene, 0.6 part of epoxy acrylate, 11 parts of benzene are stirred with the speed of 50rpm, and mixing direction, stirring are changed per 5min
After 20min, obtained 55 parts of micro/nano level CL-20 particles in previous step are added thereto to, after continuing to stir 45min, add 4
Part UV light curing agents, after continuing to stir 12min, obtain final product UV photocurings ink containing energy.
Wherein zirconium oxide ball milling pearl for diameter 3mm and diameter 1mm etc. mass mixing thing, micro/nano level CL-20 particles
Particle diameter is 600-1200nm, and UV light curing agents are Isosorbide-5-Nitrae-hydroxymethyl-cyclohexane, the oxidation of 2,4,6- trimethylbenzoyl diphenyl
The mixture of phosphorus and N- vinylpyrrolidones.
Embodiment 6
(1) 100 parts of CL-20 and 140 part of ultra-pure waters are added in ball grinder, and are added thereto to 800 parts of zirconia balls
Mill pearl, is ground with the speed of 150rpm, every 30min switching-over grindings direction, 15h is persistently ground, afterwards by the CL-20 after grinding
After suction filtration, freeze-drying under vacuum condition obtains final product micro/nano level CL-20 particles；
(2) by dry nitrocotton 1.5 parts be dissolved in 4 parts of acetone, stir, 5.5 parts are added thereto to afterwards
Styrene, 0.8 part of epoxy acrylate, 12 parts of toluene, are stirred with the speed of 45rpm, and mixing direction is changed per 5min, are stirred
After mixing 20min, obtained 50 parts of micro/nano level CL-20 particles in previous step are added thereto to, after continuing to stir 35min, plus
Enter 4 parts of UV light curing agents, after continuing to stir 10min, obtain final product UV photocurings ink containing energy.
Wherein zirconium oxide ball milling pearl for diameter 3mm and diameter 1mm etc. mass mixing thing, micro/nano level CL-20 particles
Particle diameter is 600-1200nm, and UV light curing agents are Isosorbide-5-Nitrae-hydroxymethyl-cyclohexane, the oxidation of 2,4,6- trimethylbenzoyl diphenyl
The mixture of phosphorus and N- vinylpyrrolidones.
Claims (7)
1. a kind of UV photocurings based on micro/nano level CL-20 contain the preparation method of energy ink, it is characterised in that：With parts by weight
Meter, comprises the following steps：
(1) 100 parts of CL-20 and 100-150 parts of ultra-pure waters are added in ball grinder, and are added thereto to 700-900 parts of oxidation
Zirconium ball milling pearl, is ground with the speed of 140-160rpm, every 30min switching-over grindings direction, persistently grinds 10-16h, will be ground afterwards
After CL-20 suction filtrations after mill, freeze-drying under vacuum condition obtains final product micro/nano level CL-20 particles；
(2) dry nitrocotton 1-2 parts is dissolved in 3-4 parts of acetone, is stirred, 4-6 parts of benzene is added thereto to afterwards
Ethene, 0.5-0.9 part binder, 10-13 parts of aromatic solvent, are stirred with the speed of 40-60rpm, and conversion is stirred per 5min
Direction is mixed, after stirring 20min, 40-60 parts of obtained micro/nano level CL-20 particles in previous step is added thereto to, continues to stir
After mixing 30-45min, 3-5 parts of UV light curing agent is added, after continuing to stir 10-15min, obtain final product UV photocurings ink containing energy.
2. the UV photocurings based on micro/nano level CL-20 according to claim 1 contain the preparation method of energy ink, its feature
It is：The zirconium oxide ball milling pearl for diameter 3mm and diameter 1mm etc. mass mixing thing.
3. the UV photocurings based on micro/nano level CL-20 according to claim 1 contain the preparation method of energy ink, its feature
It is：The particle diameter of the micro/nano level CL-20 particles is 600-1200nm.
4. the UV photocurings based on micro/nano level CL-20 according to claim 1 contain the preparation method of energy ink, its feature
It is：The binder is one or more mixture in HTPB, poly epihydric alcohol nitrate or epoxy acrylate.
5. the UV photocurings based on micro/nano level CL-20 according to claim 1 contain the preparation method of energy ink, its feature
It is：The aromatic solvent is benzene, toluene or dimethylbenzene.
6. the UV photocurings based on micro/nano level CL-20 according to claim 1 contain the preparation method of energy ink, its feature
It is：The UV light curing agents are Isosorbide-5-Nitrae-hydroxymethyl-cyclohexane, 2,4,6- trimethylbenzoyl diphenyl phosphate oxidations and N- second
The mixture of alkene pyrrolidone.
7. a kind of UV photocurings based on micro/nano level CL-20 contain energy ink, it is characterised in that：As described in claim 1-6
Either method is prepared from.
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| CN201611215652.2A CN106748593A (en) | 2016-12-26 | 2016-12-26 | A kind of UV photocurings based on micro/nano level CL 20 ink containing energy and preparation method thereof |
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| CN201611215652.2A CN106748593A (en) | 2016-12-26 | 2016-12-26 | A kind of UV photocurings based on micro/nano level CL 20 ink containing energy and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183291A (en) * | 2019-06-10 | 2019-08-30 | 中国工程物理研究院化工材料研究所 | A method of improving composite explosives heating conduction |
| CN111170814A (en) * | 2020-01-15 | 2020-05-19 | 中北大学 | CL-20-based energetic film spraying material and micro-spraying direct-writing forming method |
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| CN103351837A (en) * | 2013-05-10 | 2013-10-16 | 北京理工大学 | Non-ester plasticizer-containing energetic material casting curing system and curing method thereof |
| 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 |
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2016
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| CN101418157A (en) * | 2008-12-11 | 2009-04-29 | 中国科学院化学研究所 | Nano pigment ink for direct plate making of ink jet printing computer and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183291A (en) * | 2019-06-10 | 2019-08-30 | 中国工程物理研究院化工材料研究所 | A method of improving composite explosives heating conduction |
| CN110183291B (en) * | 2019-06-10 | 2021-03-16 | 中国工程物理研究院化工材料研究所 | Method for improving thermal conductivity of mixed explosive |
| CN111170814A (en) * | 2020-01-15 | 2020-05-19 | 中北大学 | CL-20-based energetic film spraying material and micro-spraying direct-writing forming method |
| CN111170814B (en) * | 2020-01-15 | 2021-06-01 | 中北大学 | CL-20-based energetic film spraying material and micro-spraying direct-writing forming method |
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