CN115259976A - High polymer bonded explosive and preparation method and application thereof - Google Patents
High polymer bonded explosive and preparation method and application thereof Download PDFInfo
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- CN115259976A CN115259976A CN202211077861.0A CN202211077861A CN115259976A CN 115259976 A CN115259976 A CN 115259976A CN 202211077861 A CN202211077861 A CN 202211077861A CN 115259976 A CN115259976 A CN 115259976A
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- 239000002360 explosive Substances 0.000 title claims abstract description 114
- 229920000642 polymer Polymers 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002135 nanosheet Substances 0.000 claims abstract description 41
- 229910052582 BN Inorganic materials 0.000 claims abstract description 30
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 27
- 229940090898 Desensitizer Drugs 0.000 claims abstract description 23
- 239000000853 adhesive Substances 0.000 claims abstract description 22
- 230000001070 adhesive effect Effects 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 12
- 238000003776 cleavage reaction Methods 0.000 claims description 11
- 230000007017 scission Effects 0.000 claims description 11
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 8
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000004449 solid propellant Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical class [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229960001701 chloroform Drugs 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000003975 dentin desensitizing agent Substances 0.000 claims 1
- 239000002055 nanoplate Substances 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 239000011229 interlayer Substances 0.000 abstract description 3
- 238000009825 accumulation Methods 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 27
- 239000000243 solution Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 14
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 description 13
- 238000000113 differential scanning calorimetry Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000011085 pressure filtration Methods 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 238000000089 atomic force micrograph Methods 0.000 description 6
- 238000004108 freeze drying Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- NDYLCHGXSQOGMS-UHFFFAOYSA-N CL-20 Chemical compound [O-][N+](=O)N1C2N([N+]([O-])=O)C3N([N+](=O)[O-])C2N([N+]([O-])=O)C2N([N+]([O-])=O)C3N([N+]([O-])=O)C21 NDYLCHGXSQOGMS-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 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 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Images
Classifications
-
- 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
- C06B23/005—Desensitisers, phlegmatisers
-
- 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
- C06B23/001—Fillers, gelling and thickening agents (e.g. fibres), absorbents for nitroglycerine
-
- 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
Abstract
The invention belongs to the technical field of explosives, and particularly relates to a high polymer bonded explosive as well as a preparation method and application thereof. The invention provides a high polymer bonded explosive which comprises the following components in percentage by mass: 93-96% of main explosive, 3-6% of adhesive and 1-3% of desensitizer, wherein the desensitizer comprises hexagonal boron nitride nanosheets or graphene nanosheets. In the invention, the hexagonal boron nitride nanosheets and the graphene nanosheets are two-dimensional layered materials, the surfaces of the hexagonal boron nitride nanosheets and the graphene nanosheets have rich functional groups, the interlayer acting force is weak, and the sliding is easy. According to the invention, the sensitivity reducing agent with excellent heat conduction performance is introduced into the high polymer bonded explosive, so that the high polymer bonded explosive is easy to generate micro-flow deformation when being stimulated by the outside, and the generation of effective 'hot spots' and the probability of further heat accumulation are reduced, thereby improving the mechanical sensitivity and the thermal stability of the high polymer bonded explosive and improving the safety of the high polymer bonded explosive.
Description
Technical Field
The invention belongs to the technical field of explosives, and particularly relates to a high polymer bonded explosive as well as a preparation method and application thereof.
Background
The core of the insensitive ammunition is an insensitive energetic material which is a necessary condition for realizing the insensitivity of the ammunition of the weapon. HMX is the explosive with the best comprehensive performance in use at present, has the advantages of high density, high detonation heat, good chemical stability and the like, and is widely applied to the fields of missile warheads, initiation explosive charging, solid propellants and the like. However, HMX has high mechanical sensitivity, and in order to improve the defect of high mechanical sensitivity, a binding agent is usually used to coat the surface of HMX to form a high polymer bonded explosive.
However, the existing high polymer bonded explosive still has difficulty in meeting the requirement of maintaining high stability and safety under the production, storage, transportation, use and battlefield environments, and the stability and safety of the existing high polymer bonded explosive under external stimuli such as temperature change, impact or vibration and the like still needs to be further improved.
Disclosure of Invention
In view of the above, the invention provides a high polymer bonded explosive, a preparation method and an application thereof, and the high polymer bonded explosive provided by the invention has lower mechanical sensitivity and good thermal stability, and the safety is improved.
In order to solve the technical problems, the invention provides a high polymer bonded explosive which comprises the following components in percentage by mass:
93-96% of main explosive;
3 to 6 percent of adhesive;
1 to 3 percent of desensitizer;
the desensitizer comprises hexagonal boron nitride nanosheets or graphene nanosheets.
Preferably, the average thickness of the hexagonal boron nitride nanosheets and the average thickness of the graphene nanosheets are independently 1-10 nm.
Preferably, the desensitizer is prepared by the following method:
dispersing hexagonal boron nitride or graphene in an organic solvent, and performing ultrasonic cleavage to obtain the desensitizer;
the organic solvent comprises one or more of N, N-dimethylformamide, trichloromethane, 1,2-dichloroethane and methane sulfonic acid.
Preferably, the power of ultrasonic cleavage is 600-800W, and the time of ultrasonic cleavage is 8-10 h.
Preferably, the binder includes one or more of ethylene-vinyl acetate copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, and acrylate rubber.
The invention also provides a preparation method of the high polymer bonded explosive in the technical scheme, which comprises the following steps:
mixing the main explosive, the desensitizer and water to obtain a suspension;
and (4) dropwise adding an adhesive solution into the suspension for coating to obtain the high polymer bonded explosive.
Preferably, the mixing is carried out under the condition of stirring, the stirring temperature is 50-65 ℃, and the stirring rotating speed is 300-600 r/min.
Preferably, the mass concentration of the adhesive solution is 3-5%; the solvent in the binder solution comprises one or more of 1,2-dichloroethane, ethyl acetate, and acetone.
Preferably, the dropping speed is 1.8-2.2 mL/min;
the dripping is carried out under the vacuum condition, and the vacuum degree of the vacuum condition is-0.02 to-0.06 Mpa.
The invention also provides the application of the high polymer bonded explosive prepared by the technical scheme or the preparation method in the technical scheme in the insensitive solid propellant or the insensitive press-fitting explosive.
The invention provides a high polymer bonded explosive which comprises the following components in percentage by mass: 93-96% of main explosive, 3-6% of adhesive and 1-3% of sensitivity reducing agent, wherein the sensitivity reducing agent comprises hexagonal boron nitride nanosheets or graphene nanosheets. In the invention, the hexagonal boron nitride nanosheets and the graphene nanosheets are two-dimensional layered materials, the surfaces of the hexagonal boron nitride nanosheets and the graphene nanosheets are rich in functional groups, the interlayer acting force is weak, the sliding is easy, and the hexagonal boron nitride nanosheets and the graphene nanosheets have excellent heat conduction performance. According to the invention, the sensitivity reducing agent with a two-dimensional layered structure and excellent heat conductivity is introduced into the high polymer bonded explosive, so that the high polymer bonded explosive is easy to generate micro-flow deformation when being stimulated by the outside, and the generation of effective 'hot spots' and the probability of further heat accumulation are reduced, thereby improving the mechanical sensitivity and the thermal stability of the high polymer bonded explosive and improving the safety of the high polymer bonded explosive.
Drawings
FIG. 1 is an Atomic Force Microscope (AFM) image of hexagonal boron nitride nanoplates prepared in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the high polymer bonded explosive prepared in example 1;
FIG. 3 is a Differential Scanning Calorimetry (DSC) plot of the high polymer bound explosive prepared in example 1, wherein β is the rate of temperature increase;
FIG. 4 is an AFM image of graphene nanoplatelets prepared according to example 2;
FIG. 5 is an SEM image of the high polymer bonded explosive prepared in example 2;
FIG. 6 is a DSC of the high polymer bonded explosive prepared in example 2, wherein β is the rate of temperature increase;
FIG. 7 is an SEM image of a high polymer bound explosive prepared in comparative example 1;
FIG. 8 is a DSC of the high polymer bound explosive prepared in comparative example 1, where β is the rate of temperature increase;
FIG. 9 is an AFM image of hexagonal boron nitride nanoplates prepared in comparative example 3;
FIG. 10 is an SEM image of a high polymer bound explosive prepared in comparative example 3;
FIG. 11 is a DSC of the high polymer bound explosive prepared in comparative example 3, where β is the rate of temperature increase.
Detailed Description
The invention provides a high polymer bonded explosive which comprises the following components in percentage by mass:
93-96% of main explosive;
3 to 6 percent of adhesive;
1 to 3 percent of desensitizer;
the desensitizer comprises hexagonal boron nitride nanosheets or graphene nanosheets.
The high polymer bonded explosive comprises 93-96% of main explosive by mass percentage, and preferably 94-95%. In the present invention, the main explosive preferably comprises cyclotetramethylenetetranitramine (HMX), cyclotrimethylenetrinitramine (RDX) or hexanitrohexaazaisowurtzitane (CL-20), more preferably cyclotetramethylenetetranitramine.
The high polymer bonded explosive comprises 3-6% of a binding agent, preferably 4-5% by mass. In the present invention, the binder preferably includes ethylene-vinyl acetate copolymer (EVA), vinylidene fluoride-hexafluoropropylene copolymer (F) 2602 ) Vinylidene fluoride-chlorotrifluoroethylene copolymer (F) 2314 ) And an acrylate rubber (ACM), more preferably an ethylene-vinyl acetate copolymer. In the invention, when the adhesive comprises more than two specific substances, the proportion of the specific substances is not required to be special, and any proportion can be adopted. In the invention, the adhesive has the characteristics of high elasticity and viscoelasticity, and the mechanical strength, the processing performance and the environmental adaptability of the explosive are improved by coating the adhesive on the surfaces of the main explosive particles.
The high polymer bonded explosive comprises 1-3% of desensitizer, preferably 1-2% by mass percentage. In the present invention, the desensitizer comprises hexagonal boron nitride nanosheets or graphene nanosheets, preferably hexagonal Boron Nitride Nanosheets (BNNSs). In the invention, the desensitizer is preferably prepared according to the following method:
and dispersing hexagonal boron nitride or graphene in an organic solvent, and carrying out ultrasonic cleavage to obtain the desensitizer.
In the present invention, the organic solvent preferably includes one or more of N, N-dimethylformamide, chloroform, 1,2-dichloroethane and methanesulfonic acid, and more preferably N, N-dimethylformamide. In the present invention, the mass ratio of the hexagonal boron nitride to the graphene to the organic solvent is independently preferably 1 g.
The invention has no special requirements on the dispersion, as long as the hexagonal boron nitride or the graphene can be uniformly dispersed.
In the present invention, the power of the ultrasonic cleavage is preferably 600 to 800W, more preferably 650 to 750W; the time for ultrasonic cleavage is preferably 8 to 10 hours, and more preferably 8.5 to 9.5 hours.
In the present invention, it is preferable that after the ultrasonic cleavage, the method further comprises performing solid-liquid separation on the system after the ultrasonic cleavage to obtain the desensitizer. In the present invention, the solid-liquid separation preferably comprises centrifugation; the rotating speed of the centrifugation is preferably 6000 to 8000r/min, and more preferably 6000 to 7000r/min; the time for the centrifugation is preferably 5 to 10min, more preferably 8 to 10min.
In the present invention, the average thicknesses of the hexagonal boron nitride nanosheets and the graphene nanosheets are independently preferably 1 to 10nm, and more preferably 1 to 4nm.
In the invention, the hexagonal boron nitride nanosheets and the graphene nanosheets have good heat conduction performance and mechanical strength within the thickness range, and the probability of generating effective hot spots on the surface of the explosive crystal can be effectively reduced, so that the effect of reducing the sense of the high polymer bonded explosive is realized.
In the present invention, the average particle size of the polymer bonded explosive is preferably 300 to 1000. Mu.m, more preferably 500 to 700. Mu.m.
The invention utilizes the adhesive to coat the desensitizer on the surface of the main explosive crystal, improves the thermal stability of the high polymer bonded explosive and solves the technical problem of insufficient safety performance of the existing high polymer bonded explosive.
The invention also provides a preparation method of the high polymer bonded explosive in the technical scheme, which comprises the following steps:
mixing the main explosive, the desensitizer and water to obtain a suspension;
and (4) dropwise adding an adhesive solution into the suspension for coating to obtain the high polymer bonded explosive.
According to the invention, the main explosive, the desensitizer and water are mixed to obtain the suspension. In the present invention, the water is preferably deionized water. In the present invention, the mass ratio of the total mass of the main explosive and the desensitizer to water is preferably 1:4 to 5, more preferably 1. In the present invention, the mixing is preferably performed under stirring conditions, and the stirring temperature is preferably 50 to 65 ℃, more preferably 55 to 60 ℃; the rotation speed of the stirring is preferably 300 to 600r/min, and more preferably 400 to 500r/min. The stirring time is not particularly limited, and the stirring time is not particularly limited as long as the stirring time can be uniformly mixed.
After the suspension is obtained, the invention adds the adhesive solution into the suspension for coating, and the high polymer bonded explosive is obtained. In the present invention, the binder solution is preferably obtained by dissolving a binder in a solvent. In the present invention, the solvent preferably comprises one or more of 1,2-dichloroethane, ethyl acetate and acetone, more preferably 1,2-dichloroethane. In the present invention, the mass concentration of the binder solution is preferably 3 to 5%, more preferably 4 to 5%. The invention has no special requirements on the dissolution, as long as the dissolution can be completed.
In the present invention, the rate of the dropwise addition is preferably 1.8 to 2.2mL/min, more preferably 2mL/min. In the present invention, the dropping is preferably carried out under a vacuum condition, and the degree of vacuum of the vacuum condition is preferably-0.02 to-0.06 MPa, more preferably-0.04 to-0.06 MPa. In the present invention, the dropping is preferably accompanied by stirring, and the rotation speed of the stirring is preferably 300 to 600r/min, more preferably 400 to 500r/min. In the present invention, the coating time is preferably 20 to 30min, more preferably 23 to 28min. In the present invention, the temperature of the coating is preferably 50 to 65 ℃, more preferably 55 to 60 ℃. The coating is carried out in the temperature range, so that the volatilization of the solvent is facilitated, and the coating is promoted. In the invention, after the adhesive solution is dripped into the suspension, the solvent in the mixed solution is volatilized to separate out the adhesive to coat the explosive particles and the surface of the desensitizer.
In the present invention, the suspension is clear and agglomerated white particles appear at the completion of the coating.
In the present invention, the coating preferably further comprises:
carrying out solid-liquid separation on the coated system to obtain a solid;
and washing and drying the solid to obtain the high polymer bonded explosive.
In the present invention, the solid-liquid separation preferably comprises filtration. In the present invention, the filtration is preferably suction filtration under reduced pressure; the pressure of the reduced pressure filtration is preferably-0.04 to-0.06 MPa, and more preferably-0.05 to-0.06 MPa.
In the present invention, the washing solvent is preferably water, and the water is preferably deionized water; the number of washing is preferably 2 to 3. In the present invention, the drying is preferably freeze-drying, the temperature of the freeze-drying is preferably-38 to-42 ℃, and more preferably-40 ℃; the time for the freeze-drying is preferably 46 to 50 hours, and more preferably 48 to 49 hours.
The preparation method provided by the invention has low requirements on equipment, is simple and convenient for post-treatment, and can finish the coating of the two-dimensional material and the adhesive on the surface of the explosive crystal through simple steps.
The invention also provides the application of the high polymer bonded explosive prepared by the technical scheme or the preparation method in the technical scheme in the insensitive solid propellant or the insensitive press-fitting explosive.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Dispersing 1g of hexagonal boron nitride in 40mLN, N-dimethylformamide, ultrasonically cleaving for 10 hours under the condition that the power is 650W, and centrifuging for 10 minutes under the condition that the rotating speed is 6000r/min to obtain hexagonal boron nitride nanosheets with the average thickness of 1-4 nm;
stirring 50mg of hexagonal boron nitride nanosheets, 4.7g of cyclotetramethylenetetranitramine and 20mL of deionized water at the temperature of 60 ℃ and at the rotating speed of 500r/min to obtain a suspension;
dissolving ethylene-vinyl acetate copolymer in 1,2-dichloroethane to obtain an adhesive solution with the mass concentration of 5%;
4mL of adhesive solution is dripped (with stirring at the rotating speed of 500 r/min) into the suspension for coating at the vacuum degree of-0.04 MPa and the temperature of 60 ℃ at the speed of 2mL/min; and clarifying the suspension after 10min, performing reduced pressure filtration under the pressure of-0.06 Mpa, washing the solid obtained by the reduced pressure filtration for 3 times by using deionized water, and freeze-drying at-40 ℃ for 48h to obtain the high polymer bonded explosive.
Example 2
Dispersing 1g of graphite in 40mLN, N-dimethylformamide, ultrasonically cleaving the graphite for 10 hours under the condition that the power is 650W, and centrifuging the graphite for 10 minutes under the condition that the rotating speed is 6000r/min to obtain graphene nanosheets with the average thickness of 1-4 nm;
stirring 50mg of graphene nanosheet nanosheets, 4.7g of cyclotetramethylene tetranitramine and 20mL of deionized water at the temperature of 60 ℃ and at the rotating speed of 500r/min to obtain a suspension;
dissolving ethylene-vinyl acetate copolymer in 1,2-dichloroethane to obtain an adhesive solution with the mass concentration of 5%;
4mL of adhesive solution is dripped (with stirring at the rotating speed of 500 r/min) into the suspension for coating at the vacuum degree of-0.04 MPa and the temperature of 60 ℃ at the speed of 2mL/min; and clarifying the suspension after 10min, performing reduced pressure filtration under the pressure of-0.06 Mpa, washing the solid obtained by the reduced pressure filtration for 3 times by using deionized water, and freeze-drying at-40 ℃ for 48h to obtain the high polymer bonded explosive.
Comparative example 1
Stirring 4.7g of cyclotetramethylenetetranitramine and 20mL of deionized water at the temperature of 60 ℃ and the rotating speed of 500r/min to obtain an explosive solution;
dissolving ethylene-vinyl acetate copolymer in 1,2-dichloroethane to obtain an adhesive solution with the mass concentration of 5%;
4mL of binder solution is dripped (with stirring at the rotating speed of 500 r/min) into the explosive solution for coating at the speed of 2mL/min under the condition that the vacuum degree is-0.04 MPa; and clarifying the suspension after 10min, performing reduced pressure filtration under the pressure of-0.06 Mpa, washing the solid obtained by the reduced pressure filtration with deionized water for 3 times, and freeze-drying at-40 ℃ for 48h to obtain the high polymer bonded explosive.
Comparative example 2
Cyclotetramethylenetetranitramine in example 1 was used as a comparative example.
Comparative example 3
A high polymer bonded explosive was prepared as in example 1, except that: replacing hexagonal boron nitride nanosheets with average thicknesses of 1-4 nm with hexagonal boron nitride nanosheets with average thicknesses of 20-50 nm; and ultrasonically cleaving the mixture for 5 hours under the condition that the power is 650W, and centrifuging the mixture for 10 minutes under the condition that the rotating speed is 4000r/min to obtain the hexagonal boron nitride nanosheet with the average thickness of 20-50 nm.
The hexagonal boron nitride nanosheet prepared in example 1 was observed using an atomic force microscope to give an AFM image, as shown in fig. 1. As can be seen from FIG. 1, the thickness of the hexagonal boron nitride nanosheet is 1.8-3.5 nm.
The high polymer bound explosive prepared in example 1 was observed by scanning electron microscopy to obtain an SEM image as shown in FIG. 2. As can be seen from FIG. 2, the average particle size of the polymer bonded explosive obtained in example 1 was 700. Mu.m, and the polymer bonded explosive had dense particles and smooth surface without significant wrinkles or cracks. The compact particles of the high polymer bonded explosive indicate that the porosity of the high polymer bonded explosive is low, and the smooth surface indicates that the surface defects of the high polymer bonded explosive are low, which is beneficial to improving the safety of the high polymer bonded explosive.
The graphene nanoplatelets prepared in example 2 were observed by an atomic force microscope to obtain an atomic force microscope image, as shown in fig. 4. From fig. 4, it is understood that the thickness of the graphene nanoplatelets is 1 to 3nm.
The high polymer bonded explosive prepared in example 2 was observed by a scanning electron microscope to obtain an SEM image, as shown in FIG. 5. As can be seen from FIG. 5, the average particle size of the polymer bound explosive prepared in example 2 was about 600 μm, and the particles of the polymer bound explosive were dense, smooth in surface, and free from significant wrinkles or cracks.
The high polymer bonded explosive prepared in comparative example 1 was observed by a scanning electron microscope to obtain an SEM image, as shown in fig. 7. As can be seen from FIG. 7, the polymer bonded explosive prepared in comparative example 1 has a particle size of about 500 μm, a dense particle size, a smooth surface, and no significant wrinkles or cracks.
The hexagonal boron nitride nanosheet prepared in comparative example 3 was observed using an atomic force microscope to obtain an atomic force microscope image, as shown in fig. 9. From FIG. 9, it is understood that the thickness of the hexagonal boron nitride nanosheet is 20 to 50nm.
The high polymer bonded explosive prepared in comparative example 3 was observed by a scanning electron microscope to obtain an SEM image, as shown in fig. 10. As can be seen from fig. 10, the average particle size of the polymer bonded explosive obtained in comparative example 3 was 1000 μm, and the particles of the polymer bonded explosive were relatively dense, had a smooth surface, and had slight cracks.
The high polymer bonded explosives prepared in examples 1 and 2 and comparative examples 1 and 3 were heated at different heating rates (5 ℃/min, 10 ℃/min, 15 ℃/min and 20 ℃/min), and detected by a differential scanning calorimeter to obtain a DSC chart, as shown in FIGS. 3, 6, 8 and 11, wherein β is the heating rate. Fig. 3 is a DSC diagram of the polymer bonded explosive prepared in example 1, fig. 6 is a DSC diagram of the polymer bonded explosive prepared in example 2, fig. 8 is a DSC diagram of the polymer bonded explosive prepared in comparative example 1, and fig. 11 is a DSC diagram of the polymer bonded explosive prepared in comparative example 3. Comparing the decomposition peak temperatures in fig. 3 and 6 and fig. 8 and 11, it can be seen that the decomposition peak temperatures of the high polymer bonded explosives prepared in examples 1 and 2 are higher than those of the high polymer bonded explosives prepared in comparative examples 1,2 and 3, which indicates that the high polymer bonded explosives prepared in examples 1 and 2 have improved thermal stability than those of the high polymer bonded explosives prepared in comparative examples 1,2 and 3. According to the invention, the high-thermal-conductivity two-dimensional BNNSs and the graphene are added, so that the heat transfer among HMX particles in the high polymer bonded explosive is improved, the thermal decomposition process of the HMX is delayed by inhibiting heat concentration, and the thermal stability of the high polymer bonded explosive is further improved.
Examples 1,2 and comparative examples 1,2 and 3 were tested for impact sensitivity according to standard GJB772A-97, method for explosives test 601.3, and the results are given in Table 1.
Table 1: impact sensitivity of high polymer bonded explosive
| Examples | Characteristic drop height (H) 50 /cm) |
| Example 1 | 65.6 |
| Example 2 | 56.5 |
| Comparative example 1 | 40.5 |
| Comparative example 2 | 28.2 |
| Comparative example 3 | 41.2 |
As can be seen from Table 1: the characteristic drop heights of examples 1 and 2 and comparative examples 1 and 3 are respectively improved by 37.3, 28.3, 12.3cm and 13cm compared with that of raw material HMX (comparative example 2), the impact sensitivity is respectively reduced by 132.27, 100.35, 43.61% and 46.10% compared with that of the raw material, and the mechanical safety performance of example 1 and example 2 is better than that of comparative examples 1,2 and 3. Compared with the comparative example 3, in the embodiment, the BNNSs and the graphene with the thickness of less than 10nm are used as two-dimensional layered materials, the interlayer acting force is weak, the sliding is easy, the high polymer bonded explosive is easy to generate micro-flow deformation when being stimulated by the outside, the probability of generating effective 'hot spots' and further accumulating heat is reduced, and the mechanical sensitivity of the high polymer bonded explosive is further improved.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. A high polymer bonded explosive comprises the following components in percentage by mass:
93-96% of main explosive;
3 to 6 percent of adhesive;
1 to 3 percent of desensitizer;
the desensitizer comprises hexagonal boron nitride nanosheets or graphene nanosheets.
2. The high polymer bonded explosive of claim 1, wherein the hexagonal boron nitride nanoplates and graphene nanoplates have an average thickness independently of 1 to 10nm.
3. The high polymer bound explosive of claim 1 or 2, wherein the desensitizing agent is prepared by a process comprising:
dispersing hexagonal boron nitride or graphene in an organic solvent, and performing ultrasonic cleavage to obtain the desensitizer;
the organic solvent comprises one or more of N, N-dimethylformamide, trichloromethane, 1,2-dichloroethane and methane sulfonic acid.
4. The high polymer bonded explosive according to claim 3, wherein the power of the ultrasonic cleavage is 600 to 800W, and the time of the ultrasonic cleavage is 8 to 10 hours.
5. The high polymer cohesive explosive of claim 1 wherein the binder comprises one or more of ethylene vinyl acetate copolymer, vinylidene fluoride hexafluoropropylene copolymer, vinylidene fluoride chlorotrifluoroethylene copolymer, and acrylate rubber.
6. A process for the preparation of a high polymer cohesive explosive according to any one of claims 1 to 5 comprising the steps of:
mixing the main explosive, the desensitizer and water to obtain a suspension;
and (4) dropwise adding an adhesive solution into the suspension for coating to obtain the high polymer bonded explosive.
7. The method according to claim 6, wherein the mixing is carried out under stirring at a temperature of 50 to 65 ℃ and at a rotation speed of 300 to 600r/min.
8. The preparation method according to claim 6, wherein the mass concentration of the binder solution is 3-5%; the solvent in the binder solution comprises one or more of 1,2-dichloroethane, ethyl acetate, and acetone.
9. The production method according to claim 6 or 8, wherein the dropping rate is 1.8 to 2.2mL/min;
the dripping is carried out under the vacuum condition, and the vacuum degree of the vacuum condition is-0.02 to-0.06 Mpa.
10. Use of a high polymer bonded explosive according to any one of claims 1 to 5 or a high polymer bonded explosive obtained by the process according to any one of claims 6 to 9 in a insensitive solid propellant or a insensitive pressure-loaded explosive.
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