CN108191590B - Energetic boron powder and preparation method thereof - Google Patents
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 27
- 238000001914 filtration Methods 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 23
- -1 tetrazole compounds Chemical class 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 239000012948 isocyanate Substances 0.000 claims abstract description 13
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 8
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000003852 triazoles Chemical class 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 4
- 238000012986 modification Methods 0.000 claims abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052796 boron Inorganic materials 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 12
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 239000000539 dimer Substances 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 6
- ZGZLYKUHYXFIIO-UHFFFAOYSA-N 5-nitro-2h-tetrazole Chemical compound [O-][N+](=O)C=1N=NNN=1 ZGZLYKUHYXFIIO-UHFFFAOYSA-N 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 claims description 4
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Chemical compound C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 claims description 4
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 4
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 3
- PZKFSRWSQOQYNR-UHFFFAOYSA-N 5-methyl-1h-1,2,4-triazole Chemical compound CC1=NC=NN1 PZKFSRWSQOQYNR-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 150000003851 azoles Chemical class 0.000 claims description 2
- 238000004137 mechanical activation Methods 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000002485 combustion reaction Methods 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000002360 explosive Substances 0.000 abstract description 5
- 239000004449 solid propellant Substances 0.000 abstract description 4
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000000010 aprotic solvent Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- JSOGDEOQBIUNTR-UHFFFAOYSA-N 2-(azidomethyl)oxirane Chemical compound [N-]=[N+]=NCC1CO1 JSOGDEOQBIUNTR-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- OLRXHZHVFRYMHO-UHFFFAOYSA-N [N+](=O)([O-])[O-].[K+].[B+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[K+].[B+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] OLRXHZHVFRYMHO-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N sodium azide Substances [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 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
- C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
- C06B33/08—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide with a nitrated organic compound
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B27/00—Compositions containing a metal, boron, silicon, selenium or tellurium or mixtures, intercompounds or hydrides thereof, and hydrocarbons or halogenated hydrocarbons
Abstract
The invention discloses a preparation method of energetic boron powder, which comprises the following steps: firstly, acidifying, namely dispersing boron powder in an organic solvent, adding acid, mechanically stirring and activating, filtering and drying to obtain acidified boron powder; and step two, isocyanate grafting, namely dispersing the acidified boron powder in an organic solvent subjected to anhydrous treatment, adding a compound containing bifunctional or polyfunctional isocyanate groups, reacting for a certain time, filtering and drying to obtain the isocyanate grafted boron powder. And step three, energetic modification, namely dispersing isocyanate grafted boron powder in an organic solvent subjected to anhydrous treatment, adding triazole or tetrazole compounds, reacting for a certain time, filtering, and drying to obtain energetic boron powder. The invention also provides energetic boron powder. The energetic boron powder has lower critical reaction temperature and can be used as a metal combustion agent in explosives, solid propellants and pyrotechnic compositions.
Description
Technical Field
The invention relates to an energetic material and a preparation method thereof, in particular to energetic boron powder and a preparation method thereof, and the energetic boron powder has wide application prospect in various explosives, solid propellants and pyrotechnic compositions.
Background
Modern wars put increasing demands on weapon systems, achieving high-energy and efficient destruction effects of weapon ammunitions becomes one of the main focus of attention, and improving the energy and energy utilization efficiency of energetic materials is a main technical approach. The application of highly active metal combustion agents in explosives, solid propellants and pyrotechnic compositions is a common practice. In various metal combustion agents, the combustion heat per unit mass of boron is 1.9 times that of aluminum, and the volume heat value is 1.66 times that of aluminum, so that the boron-containing aluminum-containing composite material has an excellent application prospect.
Although boron has a high combustion heat value, the melting point and the boiling point of boron are high (the melting point of boron is 2350K, the boiling point of boron is 4200K), and a compact high-boiling-point oxide film (the melting point of boron oxide is 723K, the boiling point of boron oxide is 2133K) is easily formed on the surface of boron particles, so that the contact between a combustion agent and an oxidant is isolated, the ignition of the combustion agent is hindered (the boron ignition temperature is 1900K-2500K), the self-sustaining of combustion reaction is not facilitated, the ignition combustion performance of boron is not ideal, and the energy utilization efficiency of boron is far from reaching the theoretical reaction heat value. The combustion of boron powder and aluminum powder has similar characteristics, but the ignition combustion condition is more severe. Therefore, how to improve the ignition combustion performance of boron becomes one of the key problems of improving the energy utilization efficiency of the mixed explosive, and the related technology has popularization and reference values for improving the ignition combustion performance of aluminum.
The existing method for improving ignition combustion performance of metal particles such as boron element mainly comprises the following steps: (a) ultrafine amorphous boron powder, improves the specific surface area and reduces the critical reaction temperature; (b) the surface temperature of the boron particles is increased by the heat released from the coated energetic material, such as AP, Glycidyl Azide Polyether (GAP), BAMO, potassium perchlorate, NaN3Perfluorofatty acids, etc.; (c) the coating material chemically reacts to remove oxide films on the particle surfaces, such as LiF, Viton A, silane, etc.; (d) the surface coating combustible material reacts with boron particles to generate low-ignition-point compounds, for example, magnesium, titanium and zirconium can generate low-ignition-point metal borides with boron; (e) combustion catalysts such as metal powders, oxides, salts and complexes of lithium, magnesium, titanium, zirconium, lead, copper, iron, chromium, bismuth, tin, etc. are added.
Disclosure of Invention
The invention aims to provide energy-containing boron powder and a preparation method thereof.
The invention is realized by the following steps:
a preparation method of energetic boron powder comprises the following steps:
step one, acidification
Dispersing boron powder in an organic solvent, adding acid for mechanical stirring and activation, wherein the mass ratio of the acid to the boron powder is 1/100-1/5, and filtering and drying after 10-30 hours to obtain acidified boron powder;
the organic solvent can be one of aprotic solvents such as acetone, acetonitrile, tetrahydrofuran, N-dimethylformamide, and dimethyl sulfoxide, and the acid can be sulfuric acid, hydrochloric acid, and nitric acid.
Step two, isocyanate grafting
Dispersing the acidified boron powder in an organic solvent subjected to anhydrous treatment, adding a compound containing bifunctional or polyfunctional isocyanate groups, wherein the mass ratio of the isocyanate compound to the acidified boron powder is 1/20-1/2, stirring and reacting at room temperature-70 ℃ for a certain time, and filtering and drying to obtain isocyanate grafted boron powder.
The organic solvent may be one of aprotic solvents such as acetone, acetonitrile, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, benzene, toluene, ethyl acetate, etc., and the compound containing a bifunctional or polyfunctional isocyanate group may be one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane-4, 4' -diisocyanate (MDI), dimer fatty acid diisocyanate (DDI), Hexamethylene Diisocyanate (HDI), and polymethylene polyphenyl polyisocyanate (PAPI), and the reaction time is 5 to 24 hours.
Step three, energetic modification
Dispersing isocyanate grafted boron powder in an organic solvent subjected to anhydrous treatment, adding triazole or tetrazole compounds, stirring and reacting at room temperature to 70 ℃ for a certain time, filtering and drying to obtain energetic boron powder, wherein the mass ratio of the azole compounds to the isocyanate grafted boron powder is 1/10-3/10.
The organic solvent may be one of aprotic solvents such as acetone, acetonitrile, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, benzene, toluene and ethyl acetate, the triazole or tetrazole compound may be one of 1,2, 3-triazole, 1,2, 4-triazole, 3-amino-1, 2, 4-triazole, 3-methyl-1, 2, 4-triazole, 1,2,3, 4-tetrazole, 5-amino-1, 2,3, 4-tetrazole and 5-nitro-1, 2,3, 4-tetrazole, and the reaction time is 5 to 24 hours.
Another object of the present invention is to provide an energetic boron powder.
The energy-containing boron powder is prepared by the preparation method of the energy-containing boron powder provided by the invention and has the following structure:
taking simple substance boron powder particles as a core, and taking a compound containing bifunctional or polyfunctional isocyanate groups as a connecting molecule; triazole or tetrazole compounds are taken as energetic molecules.
The energetic boron powder prepared by the method has lower critical reaction temperature and can be used as a metal combustion agent in explosives, solid propellants and pyrotechnic compositions.
Drawings
FIG. 1 is a schematic structural view of energetic boron powder.
Detailed Description
The following are some specific examples of the application of the technical solution of the present invention, which are given as examples only and are not to be construed as limiting the application of the present invention. Equivalent substitutions or equivalent exchanges of operating conditions, material compositions and proportions are within the scope of the invention.
The energetic boron powder provided by the embodiment of the invention is shown in figure 1, and the energetic boron powder takes simple substance boron powder particles as cores, takes a compound A containing bifunctional or polyfunctional isocyanate groups as a connecting molecule, and can be Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane-4, 4' -diisocyanate (MDI), dimer fatty acid diisocyanate (DDI), Hexamethylene Diisocyanate (HDI) and polymethylene polyphenyl polyisocyanate (PAPI); the triazole or tetrazole compound B is an energetic molecule and can be 1,2, 3-triazole, 1,2, 4-triazole, 3-amino-1, 2, 4-triazole, 3-methyl-1, 2, 4-triazole, 1,2,3, 4-tetrazole, 5-amino-1, 2,3, 4-tetrazole, or 5-nitro-1, 2,3, 4-tetrazole.
The invention is further illustrated below by means of several specific preparation process examples.
Example 1:
dispersing 5.0g of boron powder in 100mL of acetone, dropwise adding 0.5g of nitric acid (mass fraction is 65-68%), stirring at room temperature for 10h, filtering and drying to obtain the acidified boron powder. Adding acidified boron powder and 1.8g of toluene diisocyanate into 100mL of anhydrous toluene, stirring and reacting for 10h at 70 ℃, filtering and drying to obtain toluene diisocyanate grafted boron powder, then dispersing the toluene diisocyanate grafted boron powder into 50mL of anhydrous N, N-dimethylformamide, adding 1.0g of 1,2, 3-triazole, stirring and reacting for 10h at 50 ℃, filtering and drying to obtain about 5.2g of energetic boron powder.
Example 2:
dispersing 10.0g of boron powder in 200mL of acetone, dropwise adding 1.0g of hydrochloric acid (mass fraction is 35-37%), stirring at room temperature for 15h, filtering, and drying to obtain the acidified boron powder. Adding acidified boron powder and 4.5g of isophorone diisocyanate into 200mL of anhydrous acetonitrile, stirring and reacting for 20h at 70 ℃, filtering and drying to obtain isophorone diisocyanate grafted boron powder, then dispersing into 100mL of anhydrous acetonitrile, adding 2.0g of 3-amino 1,2, 4-triazole, stirring and reacting for 10h at 70 ℃, filtering and drying to obtain about 11.3g of energetic boron powder.
Example 3:
dispersing 5.0g of boron powder in 100mL of tetrahydrofuran, dropwise adding 0.5g of sulfuric acid (mass fraction of 30%), stirring at room temperature for 10h, filtering and drying to obtain the acidified boron powder. Adding acidified boron powder and 2.5g of diphenylmethane-4, 4 ' -diisocyanate into 100mL of anhydrous acetone, stirring and reacting for 15h at room temperature, filtering and drying to obtain diphenylmethane-4, 4 ' -diisocyanate grafted boron powder, then dispersing the diphenylmethane-4, 4 ' -diisocyanate grafted boron powder into 100mL of anhydrous acetone, adding 0.7g of 1,2,3, 4-tetrazole, stirring and reacting for 10h at room temperature, filtering and drying to obtain about 5.5g of energetic boron powder.
Example 4:
dispersing 20.0g of boron powder in 200mL of acetone, dropwise adding 1.8g of nitric acid (mass fraction is 65-68%), stirring at room temperature for 24h, filtering and drying to obtain the acidified boron powder. Adding acidified boron powder and 3.7g of toluene diisocyanate into 200mL of anhydrous toluene, stirring and reacting for 20h at 40 ℃, filtering and drying to obtain toluene diisocyanate grafted boron powder, then dispersing the toluene diisocyanate grafted boron powder into 100mL of anhydrous dimethyl sulfoxide, adding 3.0g of 5-amino-1, 2,3, 4-tetrazole, stirring and reacting for 10h at 40 ℃, filtering and drying to obtain about 22.0g of energetic boron powder.
Example 5:
dispersing 5.0g of boron powder in 100mL of acetonitrile, dropwise adding 1.0g of hydrochloric acid (mass fraction is 35-37%), stirring at room temperature for 20h, filtering, and drying to obtain the acidified boron powder. Adding acidified boron powder and 5.5g of dimer fatty acid diisocyanate into 100mL of anhydrous toluene, stirring and reacting for 10h at 60 ℃, filtering and drying to obtain dimer fatty acid diisocyanate grafted boron powder, then dispersing the dimer fatty acid diisocyanate grafted boron powder into 50mL of anhydrous dimethyl sulfoxide, adding 1.0g of 5-nitro-1, 2,3, 4-tetrazole, stirring and reacting for 20h at 60 ℃, filtering and drying to obtain about 6.5g of energetic boron powder.
Example 6:
dispersing 10.0g of boron powder in 100mL of acetone, dropwise adding 2.0g of sulfuric acid (mass fraction of 30%), stirring at room temperature for 24h, filtering and drying to obtain the acidified boron powder. Adding acidified boron powder and 4.0g of polymethylene polyphenyl polyisocyanate into 100mL of anhydrous benzene, stirring and reacting for 10h at 40 ℃, filtering and drying to obtain polymethylene polyphenyl polyisocyanate grafted boron powder, then dispersing the polymethylene polyphenyl polyisocyanate grafted boron powder into 100mL of anhydrous dimethyl sulfoxide, adding 1.0g of 5-nitro-1, 2,3, 4-tetrazole, stirring and reacting for 20h at 40 ℃, filtering and drying to obtain about 12.5g of energetic boron powder.
Applying the 6 groups of energetic boron powder to pyrotechnic composition B/KNO3Replacing common boron powder, measuring the reaction temperature by differential scanning calorimetry, and applying boron powder containing energy to make pyrotechnic composition B/KNO as shown in Table 13The critical reaction temperature is advanced by 10-30 ℃.
TABLE 1 application of B/KNO pyrotechnic compositions before and after application of energetic boron powders3Reaction temperature
| Mass ratio of boron powder to potassium nitrate | Boron powder | Reaction temperature/. degree.C |
| 1/9 | Ordinary boron powder | 570 |
| 1/9 | Example 1 | 548 |
| 2/8 | Ordinary boron powder | 540 |
| 2/8 | Example 2 | 523 |
| 3/7 | Ordinary boron powder | 537 |
| 3/7 | Example 3 | 517 |
| 3/7 | Example 4 | 525 |
| 3/7 | Example 5 | 507 |
| 5/5 | Ordinary boron powder | 510 |
| 5/5 | Example 6 | 491 |
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (5)
1. A preparation method of energetic boron powder is characterized by comprising the following steps:
step one, acidification
Dispersing boron powder in an organic solvent, adding acid for mechanical stirring and activation, wherein the mass ratio of the acid to the boron powder is 1/100-1/5, and filtering and drying after 10-30 hours to obtain acidified boron powder;
step two, isocyanate grafting
Dispersing acidified boron powder in an organic solvent subjected to anhydrous treatment, adding a compound containing bifunctional or polyfunctional isocyanate groups, wherein the mass ratio of an isocyanate compound to the acidified boron powder is 1/20-1/2, stirring and reacting at room temperature-70 ℃ for a certain time, and filtering and drying to obtain isocyanate grafted boron powder;
step three, energetic modification
Dispersing isocyanate grafted boron powder in an organic solvent subjected to anhydrous treatment, adding triazole or tetrazole compounds, stirring and reacting at room temperature to 70 ℃ for a certain time, filtering and drying to obtain energetic boron powder, wherein the mass ratio of the azole compounds to the isocyanate grafted boron powder is 1/10-3/10.
2. The method for producing an energetic boron powder according to claim 1, characterized in that:
in the first step, the organic solvent is one of acetone, acetonitrile, tetrahydrofuran, N-dimethylformamide and dimethyl sulfoxide, and the acid is one of sulfuric acid, hydrochloric acid and nitric acid.
3. The method for producing an energetic boron powder according to claim 1, characterized in that:
in the second step, the organic solvent is one of acetone, acetonitrile, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, benzene, toluene and ethyl acetate, the compound containing a bifunctional or polyfunctional isocyanate group is one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane-4, 4' -diisocyanate (MDI), dimer fatty acid diisocyanate (DDI), Hexamethylene Diisocyanate (HDI) and polymethylene polyphenyl polyisocyanate (PAPI), and the reaction time is 5-24 hours.
4. The method for producing an energetic boron powder according to claim 1, characterized in that:
in the third step, the organic solvent is one of acetone, acetonitrile, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, benzene, toluene and ethyl acetate, the triazole or tetrazole compound is one of 1,2, 3-triazole, 1,2, 4-triazole, 3-amino-1, 2, 4-triazole, 3-methyl-1, 2, 4-triazole, 1,2,3, 4-tetrazole, 5-amino-1, 2,3, 4-tetrazole and 5-nitro-1, 2,3, 4-tetrazole, and the reaction time is 5-24 hours.
5. An energetic boron powder characterized by: is prepared by the method for preparing energetic boron-containing powder according to any one of claims 1 to 4 and has the following structure:
taking simple substance boron powder particles as a core, and taking a compound containing bifunctional or polyfunctional isocyanate groups as a connecting molecule; triazole or tetrazole compounds are taken as energetic molecules.
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