CN103360189A - Method for preparing auxiliary bonding agent energy-containing thermoplastic elastomer coated ammonium nitrate explosive - Google Patents
Method for preparing auxiliary bonding agent energy-containing thermoplastic elastomer coated ammonium nitrate explosive Download PDFInfo
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- CN103360189A CN103360189A CN2013102936628A CN201310293662A CN103360189A CN 103360189 A CN103360189 A CN 103360189A CN 2013102936628 A CN2013102936628 A CN 2013102936628A CN 201310293662 A CN201310293662 A CN 201310293662A CN 103360189 A CN103360189 A CN 103360189A
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- 239000002360 explosive Substances 0.000 title claims abstract description 86
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 71
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title abstract description 6
- 239000007767 bonding agent Substances 0.000 title abstract 3
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 claims abstract description 144
- 238000002360 preparation method Methods 0.000 claims abstract description 47
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000015 trinitrotoluene Substances 0.000 claims abstract description 29
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 71
- 239000003795 chemical substances by application Substances 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000013019 agitation Methods 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 16
- JSOGDEOQBIUNTR-UHFFFAOYSA-N 2-(azidomethyl)oxirane Chemical compound [N-]=[N+]=NCC1CO1 JSOGDEOQBIUNTR-UHFFFAOYSA-N 0.000 claims description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 15
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 15
- GZYKEFWLDMDXQN-UHFFFAOYSA-N C(C)=O.[N+](=O)([O-])C1=CC(=CC(=C1)[N+](=O)[O-])[N+](=O)[O-] Chemical compound C(C)=O.[N+](=O)([O-])C1=CC(=CC(=C1)[N+](=O)[O-])[N+](=O)[O-] GZYKEFWLDMDXQN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 229920002449 FKM Polymers 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 4
- JKQXUHNOKAZKCT-UHFFFAOYSA-N 2-methyl-1,3,5-trinitrobenzene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O.CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O JKQXUHNOKAZKCT-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005266 casting Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 238000003754 machining Methods 0.000 abstract 1
- 230000035945 sensitivity Effects 0.000 description 38
- 239000000523 sample Substances 0.000 description 17
- 238000004090 dissolution Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- OJCSPXHYDFONPU-UHFFFAOYSA-N etoac etoac Chemical compound CCOC(C)=O.CCOC(C)=O OJCSPXHYDFONPU-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 238000001228 spectrum Methods 0.000 description 1
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Abstract
To solve the problems that in the prior art phenomena that the dispersibility is poor and the system viscosity is increased are easy to occur in an energy-containing thermoplastic elastomer base composite explosive preparation method, production machining is unbeneficial, and the like, the invention discloses a method for preparing an auxiliary bonding agent energy-containing thermoplastic elastomer coated ammonium nitrate explosive. A bonding agent is employed to modify the surface of an ammonium nitrate explosive, namely, a hexogen RDX grain, namely, the original polar surface is converted into non-polar or low-polarity surface; a non-polar or low-polarity energy-containing thermoplastic elastomer is wrapped on the surface of the modified RDX grain, the wrapped RDX grain is added into a 2,4,6-trinitrotoluene yellow explosive TNT so as to prepare a casting explosive which takes TNT as a carrier. The method has the beneficial technical effects that the energy-containing thermoplastic elastomer relatively completely wraps the RDX surface, the bonding force of the wrapping layer is improved, dissolving of RDX from a TNT molten liquid in the casting process is prevented, the viscosity of the system in the casting process is reduced, and the dispersity of the system is improved.
Description
Technical field
The present invention relates to a kind of technology of preparing of energetic thermoplastic elastomers base binary explosive, specially refer to the auxiliary energetic thermoplastic elastomers of a kind of linking agent and coat the ammoniumnitrate explosives preparation method.
Background technology
In molten state 2, add among 4, the 6-trotyl trinitrotoluene TNT that the castexplosives of formation take TNT as carrier such as polymkeric substance, high explosive solid phase particles, ammoniumnitrate explosives hexogen RDX have advantages of that energy is high, mechanical sensitivity is low, processing characteristics is good and with low cost.Main Problems is the technical requirements that its safety performance does not reach insensitiveness ammunition IM but castexplosive is in preparation with in using, and is mainly reflected in low, the easy embrittlement of mechanical strength.Thermoplastic elastomer TPE is a kind of macromolecular material that exists with netted non-crystalline state and cage shape crystalline form, and explosive crystal is particle studded or be coated in the netted or cage structure of polymer, can improve toughness and intensity, and reduce the impact sensitivity of explosive.Energetic thermoplastic elastomers ETPE has added in thermoplastic elastomer TPE synthetic that contain can group (as: NO
2,-N
3Deng), not only contain energy and harmless, the easy recovery of degradation production, that containing of a kind of more environmental protection can macromolecular material, this elastomerics is incorporated in the castexplosive, can obtain the novel fusion casting type desensitized explosive prescription of a class reusable edible, provide feasibility for developing green explosive of future generation, thereby had higher application prospect.Yet, less based on the applied research of the castexplosive of ETPE preparation take TNT as carrier at present, if directly be prone to the phenomenon of bad dispersibility, system viscosity increase in the matrix with energetic thermoplastic elastomers ETPE adding material, be unfavorable for complete processing and the forming materials of product.Obviously, prior art energetic thermoplastic elastomers base binary explosive preparation method exists and is prone to the phenomenon that bad dispersibility, system viscosity increase, and is unfavorable for the problems such as the complete processing of product and forming materials.
In addition, as a kind of among numerous energetic thermoplastic elastomers ETPE, polyvinyl alcohol contracting 2,4,6-trinitrobenzene acetaldehyde grafting glycidyl azide polymer PVTG has with TNT, the RDX consistency is good, heat decomposition temperature is high, the characteristics of good mechanical performance, is suitable for very much RDX is coated.Described PVTG is with PVAC polyvinylalcohol contracting 2,4,6-trinitrobenzene acetaldehyde PVTNP and number-average molecular weight are that 3068 terminal hydroxy group glycidyl azide polymer GAP is initiator, 2, the 4-tolylene diisocyanate is linking agent, dibutyl tin laurate DBTDL is catalyzer, and containing of the synthetic PVTNP grafting GAP that obtains of homogeneous phase crosslinking reaction can polymkeric substance in N,N-dimethylacetamide DMAc.
Summary of the invention
The phenomenon that is prone to bad dispersibility, system viscosity increase that exists for solving prior art energetic thermoplastic elastomers base binary explosive preparation method, be unfavorable for the problems such as the complete processing of product and forming materials, the present invention proposes the auxiliary energetic thermoplastic elastomers of a kind of linking agent and coats the ammoniumnitrate explosives preparation method.The auxiliary energetic thermoplastic elastomers of linking agent of the present invention coats the ammoniumnitrate explosives preparation method and adopts linking agent that ammoniumnitrate explosives hexogen RDX particle surface is carried out modification, even polar surfaces originally becomes nonpolar or low-pole is surperficial, RDX particle surface after modification coats nonpolar or low-pole energetic thermoplastic elastomers, RDX particle after will coating again adds 2,4, among the 6-trotyl trinitrotoluene TNT, prepare the castexplosive take TNT as carrier.
Further, the auxiliary energetic thermoplastic elastomers coating of linking agent of the present invention ammoniumnitrate explosives preparation method's linking agent comprises viton F2314 and polyurethane(s) Estane.
Further, it is polyvinyl alcohol contracting 2 that the auxiliary energetic thermoplastic elastomers of linking agent of the present invention coats the nonpolar or low-pole energetic thermoplastic elastomers of ammoniumnitrate explosives preparation method, 4,6-trinitrobenzene acetaldehyde grafting glycidyl azide polymer PVTG, described PVTG is with PVAC polyvinylalcohol contracting 2,4,6-trinitrobenzene acetaldehyde PVTNP and number-average molecular weight are that 3068 terminal hydroxy group glycidyl azide polymer GAP is initiator, 2, the 4-tolylene diisocyanate is linking agent, dibutyl tin laurate DBTDL is catalyzer, and containing of the synthetic PVTNP grafting GAP that obtains of homogeneous phase crosslinking reaction can polymkeric substance in N,N-dimethylacetamide DMAc.
Further, the median size before the auxiliary energetic thermoplastic elastomers coating of linking agent of the present invention ammoniumnitrate explosives preparation method ammoniumnitrate explosives hexogen RDX coats is 25～35 μ m.
Further, the median size after the auxiliary energetic thermoplastic elastomers coating of linking agent of the present invention ammoniumnitrate explosives preparation method ammoniumnitrate explosives hexogen RDX coats is 40～50 μ m.
Further, the auxiliary energetic thermoplastic elastomers coating of linking agent of the present invention ammoniumnitrate explosives preparation method add-on nonpolar or the low-pole energetic thermoplastic elastomers is 1%～2% weight ratio that coats rear ammoniumnitrate explosives hexogen RDX.
Further, the auxiliary energetic thermoplastic elastomers coating of linking agent of the present invention ammoniumnitrate explosives preparation method may further comprise the steps:
S1, be that the ammoniumnitrate explosives hexogen RDX of 25～35 μ m joins in the water solvent of preheating with median size, make the RDX aqeous suspension;
S2, with nonpolar or low-pole energetic thermoplastic elastomers polyvinyl alcohol contracting 2,4,6-trinitrobenzene acetaldehyde grafting glycidyl azide polymer PVTG/ polyurethane(s) Estane or PVTG/ viton F2314 are dissolved in wiring solution-forming in the ethyl acetate, and its concentration is 3～6% weight ratios; Wherein, the weight ratio of PVTG/Estane is 1: 1～3: 1, and the weight ratio of PVTG/F2314 is 1: 1～3: 1;
PVTG/Estane or the PVTG/F2314 ethyl acetate mixture of S3, slow adding step S2 preparation in ammoniumnitrate explosives hexogen RDX aqeous suspension; Wherein, the add-on of PVTG is 1%～2% weight ratio of ammoniumnitrate explosives hexogen RDX after coating;
S4, under the magnetic agitation of fixed rotating speed, RDX is kept reaction, adopt water slurry to coat;
S5, the final vacuum that is covered to complete remove ethyl acetate and obtain the binary explosive particle, and the RDX median size after the coating is 40～50 μ m;
S6, the RDX particle after will coating add among the 2，4，6-trinitrotoluene trinitrotoluene TNT, prepare the castexplosive take TNT as carrier.
Further, the stirring velocity that the auxiliary energetic thermoplastic elastomers of linking agent of the present invention coats ammoniumnitrate explosives preparation method step S4 maintenance reaction is 600～700rpm, and range of reaction temperature is 60～70 ℃, and the time range of reaction is 1～2h.
Further, the vacuum ranges of the auxiliary energetic thermoplastic elastomers coating of linking agent of the present invention ammoniumnitrate explosives preparation method step S5 vacuum removal ethyl acetate is 200～300mbar.
The useful technique effect that the auxiliary energetic thermoplastic elastomers of linking agent of the present invention coats the ammoniumnitrate explosives preparation method is with energetic thermoplastic elastomers comparatively complete coating and the raising of coating layer bonding force to be carried out in the RDX surface, make under the prerequisite that required impact sensitivity requires satisfying castexplosive, effectively prevent the stripping in the TNT fused solution of RDX in the fusion-casting process, effectively reduce the viscosity of system in the fusion-casting process, increased the dispersiveness of system.
Description of drawings
Accompanying drawing 1 is the structural representation that the auxiliary energetic thermoplastic elastomers of linking agent of the present invention coats ammoniumnitrate explosives preparation method RDX cladding;
Accompanying drawing 2 is schematic flow sheets that the auxiliary energetic thermoplastic elastomers of linking agent of the present invention coats the ammoniumnitrate explosives preparation method.
Below in conjunction with the drawings and specific embodiments the auxiliary energetic thermoplastic elastomers of linking agent of the present invention being coated the ammoniumnitrate explosives preparation method is further described.
Embodiment
Accompanying drawing 1 is the structural representation that the auxiliary energetic thermoplastic elastomers of linking agent of the present invention coats ammoniumnitrate explosives preparation method RDX cladding, and among the figure, 1 is the RDX particle, and 2 is linking agent, and 3 is nonpolar or the low-pole superpolymer.As seen from the figure, the auxiliary energetic thermoplastic elastomers of linking agent of the present invention coats the ammoniumnitrate explosives preparation method and adopts linking agent that ammoniumnitrate explosives hexogen RDX particle surface is carried out modification, even polar surfaces originally becomes nonpolar or low-pole is surperficial, RDX particle surface after modification coats nonpolar or low-pole energetic thermoplastic elastomers, RDX particle after will coating again adds 2, among 4, the 6-trotyl trinitrotoluene TNT, prepare the castexplosive take TNT as carrier.
Preferably, the linking agent that the auxiliary energetic thermoplastic elastomers of linking agent of the present invention coats the ammoniumnitrate explosives preparation method comprises viton F2314 and polyurethane(s) Estane, nonpolar or low-pole energetic thermoplastic elastomers is polyvinyl alcohol contracting 2,4,6-trinitrobenzene acetaldehyde grafting glycidyl azide polymer PVTG, wherein, described PVTG is with PVAC polyvinylalcohol contracting 2,4,6-trinitrobenzene acetaldehyde PVTNP and number-average molecular weight are that 3068 terminal hydroxy group glycidyl azide polymer GAP is initiator, 2, the 4-tolylene diisocyanate is linking agent, dibutyl tin laurate DBTDL is catalyzer, and containing of the synthetic PVTNP grafting GAP that obtains of homogeneous phase crosslinking reaction can polymkeric substance in N,N-dimethylacetamide DMAc.Wherein, add-on nonpolar or the low-pole energetic thermoplastic elastomers is 1%～2% weight ratio that coats rear ammoniumnitrate explosives hexogen RDX.
Preferably, the median size that the auxiliary energetic thermoplastic elastomers of linking agent of the present invention coats before ammoniumnitrate explosives preparation method ammoniumnitrate explosives hexogen RDX coats is 25～35 μ m, and the median size after the coating is 40～50 μ m.
Accompanying drawing 2 is schematic flow sheets that the auxiliary energetic thermoplastic elastomers of linking agent of the present invention coats the ammoniumnitrate explosives preparation method, and as seen from the figure, the auxiliary energetic thermoplastic elastomers of linking agent of the present invention coats the ammoniumnitrate explosives preparation method and may further comprise the steps:
S1, be that the ammoniumnitrate explosives hexogen RDX of 25～35 μ m joins in the water solvent of preheating with median size, make the RDX aqeous suspension;
S2, with nonpolar or low-pole energetic thermoplastic elastomers polyvinyl alcohol contracting 2,4,6-trinitrobenzene acetaldehyde grafting glycidyl azide polymer PVTG/ polyurethane(s) Estane or PVTG/ viton F2314 are dissolved in wiring solution-forming in the ethyl acetate, and its concentration is 3～6% weight ratios; Wherein, the weight ratio of PVTG/Estane is 1: 1～3: 1, and the weight ratio of PVTG/F2314 is 1: 1～3: 1;
PVTG/Estane or the PVTG/F2314 ethyl acetate mixture of S3, slow adding step S2 preparation in ammoniumnitrate explosives hexogen RDX aqeous suspension; Wherein, the add-on of PVTG is 1%～2% weight ratio of ammoniumnitrate explosives hexogen RDX after coating;
S4, under the magnetic agitation of fixed rotating speed, RDX is kept reaction, adopt water slurry to coat;
S5, the final vacuum that is covered to complete remove ethyl acetate and obtain the binary explosive particle, and the RDX median size after the coating is 40～50 μ m;
S6, the RDX particle after will coating add among the 2，4，6-trinitrotoluene trinitrotoluene TNT, prepare the castexplosive take TNT as carrier.
Preferably, it is 600～700rpm that step S4 keeps the stirring velocity of reaction, and range of reaction temperature is 60～70 ℃, and the time range of reaction is 1～2h; The vacuum ranges of step S5 vacuum removal ethyl acetate is 200～300mbar.
Embodiment 1
Be that the ammoniumnitrate explosives hexogen RDX of 30 μ m adds in the water solvent of preheating with the 30g median size, with polyvinyl alcohol contracting 2,4,6-trinitrobenzene acetaldehyde grafting glycidyl azide polymer PVTG is dissolved in the superpolymer that is made into 4% concentration in the ethyl acetate-ethyl acetate miscible fluid, leaves standstill 10min in ultrasonic oscillator after the accelerate dissolution.Be under the 600rpm at the magnetic agitation rotating speed, temperature of reaction is under 70 ℃ of conditions, in ammoniumnitrate explosives hexogen RDX aqeous suspension, slowly add superpolymer-ethyl acetate mixture, its add-on accounts for the weight 1.5% that coats rear RDX with superpolymer and is as the criterion, the time of reaction is 2h, adopts water slurry that RDX is coated, then, be to carry out drying under the vacuum condition of 250mbar in vacuum tightness, obtain the RDX/PVTG sample.
Adopt the atomic mass mark of X-ray photoelectric power spectrum XPS working sample surface portion element.Massfraction by the N atom of sample surfaces calculates RDX surface coverage degree, and the definition coverage degree is R=(N
0-N
x)/N
0, wherein R is coverage degree, N
0For not coating sample surfaces N atomic mass percentage ratio, N
xFor coating rear sample surfaces N atomic mass percentage ratio.The calculation result of coverage degree R is listed in table 1.
Adopt impact sensitivity and the characteristic drop height H of WL-1 type H3.5-10W drop hammer type collision sensitivity instrument working sample
50, according to impact sensitivity (i.e. bump blast percentage) and the characteristic drop height H of the difference of 601.1 and 601.2 test methods in GJB772A-97 standard working sample
50(when namely bump blast percentage ratio is 50% corresponding drop height), every sample takes by weighing 35 ± 1mg explosive, and 25 every group, test-results is listed in table 2.
Adopt WM-1 type friction sensitivity instrument to measure friction sensitivity, according to 602.1 test methods in the GJB772A-97 standard, sensibility instrument pendulum mass quality is 2700 ± 27g, the pendulum quality is 1500 ± 10g, two groups in each sample, 25 every group, every dose is 30 ± 1mg, represent the friction sensitivity of explosive with friction blast percentage, experimental data is listed in table 2.
Embodiment 2
Be that the RDX of 35 μ m adds in the water solvent of preheating with the 30g median size, PVTG and F2314 are dissolved in the superpolymer-ethyl acetate mixture that is made into 5% concentration in the ethyl acetate by the mass ratio of 1:1, after the magnetic agitation assist in dissolving, continue to be positioned over and leave standstill 10min in the ultrasonic oscillator after the accelerate dissolution.Be under the 700rpm at the magnetic agitation rotating speed, temperature of reaction is under 60 ℃ of conditions, in ammoniumnitrate explosives hexogen RDX aqeous suspension, slowly add superpolymer-ethyl acetate mixture, its add-on accounts for the weight 2% that coats rear RDX with superpolymer and is as the criterion, the time of reaction is 1.5h, adopts water slurry that RDX is coated, then, be to carry out drying under the vacuum condition of 300mbar in vacuum tightness, obtain the RDX/PVTG/F2314 sample.Press embodiment 1 described mensuration coverage degree R, characteristic drop height H
50, impact sensitivity and friction sensitivity, the results are shown in table 1 and table 2.
Embodiment 3
Be that the RDX of 25 μ m adds in the water solvent of preheating with the 30g median size, PVTG and F2314 are dissolved in the superpolymer-ethyl acetate mixture that is made into 3% concentration in the ethyl acetate by the mass ratio of 2:1, after the magnetic agitation assist in dissolving, in ultrasonic oscillator, leave standstill 10min after the accelerate dissolution.Be under the 650rpm at the magnetic agitation rotating speed, temperature of reaction is under 65 ℃ of conditions, in ammoniumnitrate explosives hexogen RDX aqeous suspension, slowly add superpolymer-ethyl acetate mixture, its add-on accounts for the weight 1% that coats rear RDX with superpolymer and is as the criterion, the time of reaction is 1h, adopts water slurry that RDX is coated, then, be to carry out drying under the vacuum condition of 200mbar in vacuum tightness, obtain the RDX/PVTG/F2314 sample.Press embodiment 1 described mensuration coverage degree R, characteristic drop height H
50, impact sensitivity and friction sensitivity, the results are shown in table 1 and table 2.
Embodiment 4
Be that the RDX of 30 μ m adds in the water solvent of preheating with the 30g median size, PVTG and F2314 are dissolved in the solution that is made into 6% concentration in the ethyl acetate by the mass ratio of 3:1, after the magnetic agitation assist in dissolving, in ultrasonic oscillator, leave standstill 10min after the accelerate dissolution.Be under the 700rpm at the magnetic agitation rotating speed, temperature of reaction is under 70 ℃ of conditions, in ammoniumnitrate explosives hexogen RDX aqeous suspension, slowly add superpolymer-ethyl acetate mixture, its add-on accounts for the weight 1.5% that coats rear RDX with superpolymer and is as the criterion, the time of reaction is 2h, adopts water slurry that RDX is coated, then, be to carry out drying under the vacuum condition of 300mbar in vacuum tightness, obtain the RDX/PVTG/F2314 sample.Press embodiment 1 described mensuration coverage degree R, characteristic drop height H
50, impact sensitivity and friction sensitivity, the results are shown in table 1 and table 2.
Embodiment 5
Be that the RDX of 28 μ m adds in the water solvent of preheating with the 30g median size, PVTG and F2314 are dissolved in the solution that is made into 3% concentration in the ethyl acetate by the mass ratio of 3:2, after the magnetic agitation assist in dissolving, in ultrasonic oscillator, leave standstill 10min after the accelerate dissolution.Be under the 600rpm at the magnetic agitation rotating speed, temperature of reaction is under 65 ℃ of conditions, in ammoniumnitrate explosives hexogen RDX aqeous suspension, slowly add superpolymer-ethyl acetate mixture, its add-on accounts for the weight 1.5% that coats rear RDX with superpolymer and is as the criterion, the time of reaction is 1.5h, adopts water slurry that RDX is coated, then, be to carry out drying under the vacuum condition of 300mbar in vacuum tightness, obtain the RDX/PVTG/F2314 sample.Press embodiment 1 described mensuration coverage degree R, characteristic drop height H
50, impact sensitivity and friction sensitivity, the results are shown in table 1 and table 2.
Embodiment 6
Be that the RDX of 32 μ m adds in the water solvent of preheating with the 30g median size, PVTG and Estane are dissolved in the solution that is made into 6% concentration in the ethyl acetate by the mass ratio of 1:1, after the magnetic agitation assist in dissolving, in ultrasonic oscillator, leave standstill 10min after the accelerate dissolution.Be under the 700rpm at the magnetic agitation rotating speed, temperature of reaction is under 60 ℃ of conditions, in ammoniumnitrate explosives hexogen RDX aqeous suspension, slowly add superpolymer-ethyl acetate mixture, its add-on accounts for the weight 1.8% that coats rear RDX with superpolymer and is as the criterion, the time of reaction is 1.6h, adopts water slurry that RDX is coated, then, be to carry out drying under the vacuum condition of 280mbar in vacuum tightness, obtain the RDX/PVTG/Estane sample.Press embodiment 1 described mensuration coverage degree R, characteristic drop height H
50, impact sensitivity and friction sensitivity, the results are shown in table 1 and table 2.
Embodiment 7
Be that the RDX of 27 μ m adds in the water solvent of preheating with the 30g median size, PVTG and Estane are dissolved in the solution that is made into 3.5% concentration in the ethyl acetate by the mass ratio of 2:1, after the magnetic agitation assist in dissolving, in ultrasonic oscillator, leave standstill 10min after the accelerate dissolution.Be under the 620rpm at the magnetic agitation rotating speed, temperature of reaction is under 64 ℃ of conditions, in ammoniumnitrate explosives hexogen RDX aqeous suspension, slowly add superpolymer-ethyl acetate mixture, its add-on accounts for the weight 1.4% that coats rear RDX with superpolymer and is as the criterion, the time of reaction is 2h, adopts water slurry that RDX is coated, then, be to carry out drying under the vacuum condition of 230mbar in vacuum tightness, obtain the RDX/PVTG/Estane sample.Press embodiment 1 described mensuration coverage degree R, characteristic drop height H
50, impact sensitivity and friction sensitivity, the results are shown in table 1 and table 2.
Embodiment 8
Be that the RDX of 26 μ m adds in the water solvent of preheating with the 30g median size, PVTG and Estane are dissolved in the solution that is made into 6% concentration in the ethyl acetate by the mass ratio of 3:1, after the magnetic agitation assist in dissolving, in ultrasonic oscillator, leave standstill 10min after the accelerate dissolution.Be under the 700rpm at the magnetic agitation rotating speed, temperature of reaction is under 70 ℃ of conditions, in ammoniumnitrate explosives hexogen RDX aqeous suspension, slowly add superpolymer-ethyl acetate mixture, its add-on accounts for the weight 1.4% that coats rear RDX with superpolymer and is as the criterion, the time of reaction is 1.2h, adopts water slurry that RDX is coated, then, be to carry out drying under the vacuum condition of 250mbar in vacuum tightness, obtain the RDX/PVTG/Estane sample.Press embodiment 1 described mensuration coverage degree R, characteristic drop height H
50, impact sensitivity and friction sensitivity, the results are shown in table 1 and table 2.
Embodiment 9
Be that the RDX of 30 μ m adds in the water solvent of preheating with the 30g median size, PVTG and Estane are dissolved in the solution that is made into 4% concentration in the ethyl acetate by the mass ratio of 3:2, after the magnetic agitation assist in dissolving, in ultrasonic oscillator, leave standstill 10min after the accelerate dissolution.Be under the 700rpm at the magnetic agitation rotating speed, temperature of reaction is under 65 ℃ of conditions, in ammoniumnitrate explosives hexogen RDX aqeous suspension, slowly add superpolymer-ethyl acetate mixture, its add-on accounts for the weight 2% that coats rear RDX with superpolymer and is as the criterion, the time of reaction is 2h, adopts water slurry that RDX is coated, then, be to carry out drying under the vacuum condition of 300mbar in vacuum tightness, obtain the RDX/PVTG/Estane sample.Press embodiment 1 described mensuration coverage degree R, characteristic drop height H
50, impact sensitivity and friction sensitivity, the results are shown in table 1 and table 2.
Comparative Examples 1
Median size is the RDX of 30 μ m, makes blank sample.Press embodiment 1 described mensuration coverage degree R, characteristic drop height H
50, impact sensitivity and friction sensitivity, the results are shown in table 1 and table 2.
Comparative Examples 2
Polyvinyl alcohol contracting 2,4,6-trinitrobenzene acetaldehyde grafting glycidyl azide polymer PVTG makes blank sample.Press embodiment 1 described mensuration characteristic drop height H50, impact sensitivity and friction sensitivity, the results are shown in table 2.Wherein, impact sensitivity and friction sensitivity are 0 to represent very insensitiveness.
Table 1: coverage degree R detected result
Table 2: characteristic drop height H
50, impact sensitivity and friction sensitivity detected result
By above detected result as can be known, the auxiliary energetic thermoplastic elastomers of linking agent of the present invention coats the ammoniumnitrate explosives preparation method and adopts linking agent to the RDX modifying surface, make original polar surfaces become nonpolar or low-pole surperficial, the outside coats the energetic thermoplastic elastomers of nonpolar or low-pole again, in order to conform to interfacial tension with elastomeric polarity with coating, make both more firmly combinations, the energetic thermoplastic elastomers that coats and bonded layer have than RDX surface binding ability more firmly, reach toughness reinforcing, increase the effect of bullet and visbreaking.Simultaneously, can also Effective Raise coverage degree R, make coverage degree R from original 36.38%(embodiment 1) be increased to 70%～82%(embodiment 2 to 9).In specific embodiment, the energetic thermoplastic elastomers that adopts is polyvinyl alcohol contracting 2,4,6-trinitrobenzene acetaldehyde grafting glycidyl azide polymer PVTG, and two kinds of linking agents that adopt are respectively viton F2314 and polyurethane Estane.Through detecting as can be known, the auxiliary energetic thermoplastic elastomers of linking agent of the present invention coats the ammoniumnitrate explosives preparation method, adopts the better heat stability of the binary explosive that coats behind the linking agent, and its melt temperature is 206 ℃～208 ℃, a little more than 205 ℃ of RDX; Heat decomposition temperature is 240 ℃～241 ℃, with 239 ℃ of RDX quite.Impact sensitivity and the friction sensitivity of the RDX particle of the auxiliary energetic thermoplastic elastomers coating of linking agent of the present invention ammoniumnitrate explosives preparation method's coating have reduced by 50% with the RDX Particle Phase that pure energetic thermoplastic elastomers coats than all, be lower than pure RDX particle, can satisfy castexplosive and make required impact sensitivity requirement.
The auxiliary energetic thermoplastic elastomers of linking agent of the present invention coats the ammoniumnitrate explosives preparation method after obtaining the coating RDX particle, adopt the RDX particle after the common process technology will coat to add 2, among 4, the 6-trotyl trinitrotoluene TNT, prepare the castexplosive take TNT as carrier.Because the raising of RDX particle coverage degree and the mortise of coating layer, Effective Raise the thermostability of RDX particle after coating, prevent the stripping in the TNT fused solution of RDX in the fusion-casting process, reduced the viscosity of system in the fusion-casting process, increased the dispersiveness of system, and impact sensitivity also greatly reduces, for the preparation of castexplosive provides preferably processing condition.
Obviously, the useful technique effect that the auxiliary energetic thermoplastic elastomers of linking agent of the present invention coats the ammoniumnitrate explosives preparation method is with energetic thermoplastic elastomers comparatively complete coating and the raising of coating layer bonding force to be carried out in the RDX surface, make under the prerequisite that required impact sensitivity requires satisfying castexplosive, effectively prevent the stripping in the TNT fused solution of RDX in the fusion-casting process, effectively reduce the viscosity of system in the fusion-casting process, increased the dispersiveness of system.
Claims (10)
1. the auxiliary energetic thermoplastic elastomers of linking agent coats the ammoniumnitrate explosives preparation method, it is characterized in that, adopt linking agent that ammoniumnitrate explosives hexogen RDX particle surface is carried out modification, even polar surfaces originally becomes nonpolar or low-pole is surperficial, RDX particle surface after modification coats nonpolar or low-pole energetic thermoplastic elastomers, and the RDX particle after will coating again adds 2,4, among the 6-trotyl trinitrotoluene TNT, prepare the castexplosive take TNT as carrier.
2. the auxiliary energetic thermoplastic elastomers of described linking agent coats the ammoniumnitrate explosives preparation method according to claim 1, it is characterized in that, linking agent comprises viton F2314 and polyurethane(s) Estane.
3. the auxiliary energetic thermoplastic elastomers of described linking agent coats the ammoniumnitrate explosives preparation method according to claim 1, it is characterized in that, nonpolar or low-pole energetic thermoplastic elastomers is polyvinyl alcohol contracting 2,4,6-trinitrobenzene acetaldehyde grafting glycidyl azide polymer PVTG.
4. the auxiliary energetic thermoplastic elastomers of described linking agent coats the ammoniumnitrate explosives preparation method according to claim 3, it is characterized in that, nonpolar or low-pole energetic thermoplastic elastomers is polyvinyl alcohol contracting 2,4,6-trinitrobenzene acetaldehyde grafting glycidyl azide polymer PVTG is with PVAC polyvinylalcohol contracting 2,4,6-trinitrobenzene acetaldehyde PVTNP and number-average molecular weight are that 3068 terminal hydroxy group glycidyl azide polymer GAP is initiator, 2, the 4-tolylene diisocyanate is linking agent, dibutyl tin laurate DBTDL is catalyzer, and containing of the synthetic PVTNP grafting GAP that obtains of homogeneous phase crosslinking reaction can polymkeric substance in N,N-dimethylacetamide DMAc.
5. the auxiliary energetic thermoplastic elastomers of described linking agent coats the ammoniumnitrate explosives preparation method according to claim 1, it is characterized in that, the median size before hexogen RDX coats is 25～35 μ m.
6. the auxiliary energetic thermoplastic elastomers of described linking agent coats the ammoniumnitrate explosives preparation method according to claim 1, it is characterized in that, the median size after hexogen RDX coats is 40～50 μ m.
7. the auxiliary energetic thermoplastic elastomers of described linking agent coats the ammoniumnitrate explosives preparation method according to claim 1, it is characterized in that, 1%～2% weight ratio that add-on nonpolar or the low-pole energetic thermoplastic elastomers is ammoniumnitrate explosives hexogen RDX after coating.
8. the auxiliary energetic thermoplastic elastomers of described linking agent coats the ammoniumnitrate explosives preparation method according to claim 1, it is characterized in that, this preparation method may further comprise the steps:
S1, be that the ammoniumnitrate explosives hexogen RDX of 25～35 μ m joins in the water solvent of preheating with median size, make the RDX aqeous suspension;
S2, with nonpolar or low-pole energetic thermoplastic elastomers polyvinyl alcohol contracting 2,4,6-trinitrobenzene acetaldehyde grafting glycidyl azide polymer PVTG/ polyurethane(s) Estane or PVTG/ viton F2314 are dissolved in wiring solution-forming in the ethyl acetate, and its concentration is 3～6% weight ratios; Wherein, the weight ratio of PVTG/Estane is 1: 1～3: 1, and the weight ratio of PVTG/F2314 is 1: 1～3: 1;
PVTG/Estane or the PVTG/F2314 ethyl acetate mixture of S3, slow adding step S2 preparation in ammoniumnitrate explosives hexogen RDX aqeous suspension; Wherein, the add-on of PVTG is 1%～2% weight ratio of ammoniumnitrate explosives hexogen RDX after coating;
S4, under the magnetic agitation of fixed rotating speed, RDX is kept reaction, adopt water slurry to coat;
S5, the final vacuum that is covered to complete remove ethyl acetate and obtain the binary explosive particle, and the RDX median size after the coating is 40～50 μ m;
S6, the RDX particle after will coating add among the 2，4，6-trinitrotoluene trinitrotoluene TNT, prepare the castexplosive take TNT as carrier.
9. the auxiliary energetic thermoplastic elastomers of described linking agent coats the ammoniumnitrate explosives preparation method according to claim 8, it is characterized in that, it is 600～700rpm that step S4 keeps the stirring velocity of reaction, and range of reaction temperature is 60～70 ℃, and the time range of reaction is 1～2h.
10. the auxiliary energetic thermoplastic elastomers of described linking agent coats the ammoniumnitrate explosives preparation method according to claim 8, it is characterized in that, the vacuum ranges of step S5 vacuum removal ethyl acetate is 200～300mbar.
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| CN107986921A (en) * | 2017-11-28 | 2018-05-04 | 中国工程物理研究院化工材料研究所 | A kind of method for coating of TATB planes of crystal |
| CN107986925B (en) * | 2017-11-28 | 2019-12-24 | 中国工程物理研究院化工材料研究所 | High-energy-density reactive elastomer and preparation method thereof |
| CN112500253A (en) * | 2020-12-02 | 2021-03-16 | 湖北航天化学技术研究所 | Temperature-sensitive time-varying high-energy solid propellant |
| CN114874057A (en) * | 2022-04-22 | 2022-08-09 | 中北大学 | Press-fitting insensitive high polymer bonded explosive and preparation method thereof |
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