EP3611152B1 - Method for manufacturing compressed composite gunpowder using polymer emulsion, and compressed composite gunpowder manufactured thereby - Google Patents
Method for manufacturing compressed composite gunpowder using polymer emulsion, and compressed composite gunpowder manufactured thereby Download PDFInfo
- Publication number
- EP3611152B1 EP3611152B1 EP18784066.5A EP18784066A EP3611152B1 EP 3611152 B1 EP3611152 B1 EP 3611152B1 EP 18784066 A EP18784066 A EP 18784066A EP 3611152 B1 EP3611152 B1 EP 3611152B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- explosive
- emulsion
- agglomerated particles
- slurry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 66
- 238000000034 method Methods 0.000 title claims description 52
- 239000000839 emulsion Substances 0.000 title claims description 43
- 229920000642 polymer Polymers 0.000 title claims description 28
- 239000002131 composite material Substances 0.000 title claims 7
- 239000003721 gunpowder Substances 0.000 title claims 7
- 239000002360 explosive Substances 0.000 claims description 88
- 239000002245 particle Substances 0.000 claims description 71
- 229920005596 polymer binder Polymers 0.000 claims description 50
- 239000002491 polymer binding agent Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000004014 plasticizer Substances 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 25
- 239000003995 emulsifying agent Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 19
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 10
- 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 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 8
- 229920000459 Nitrile rubber Polymers 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 7
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 235000011148 calcium chloride Nutrition 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 5
- 229920000800 acrylic rubber Polymers 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 235000002639 sodium chloride Nutrition 0.000 claims description 5
- RJLCAYZZHSLQLN-UHFFFAOYSA-N 10-methylundecyl nonanoate Chemical compound C(CCCCCCCC)(=O)OCCCCCCCCCC(C)C RJLCAYZZHSLQLN-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 229920002367 Polyisobutene Polymers 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 239000005060 rubber Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- AXSWSZNOMAPDQD-UHFFFAOYSA-M acetyl-benzyl-dimethylazanium;chloride Chemical compound [Cl-].CC(=O)[N+](C)(C)CC1=CC=CC=C1 AXSWSZNOMAPDQD-UHFFFAOYSA-M 0.000 claims description 3
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 3
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 235000007715 potassium iodide Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 235000011147 magnesium chloride Nutrition 0.000 claims description 2
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 description 18
- 230000035945 sensitivity Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- 238000004880 explosion Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000035939 shock Effects 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000693 micelle Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007767 bonding agent Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000005303 weighing 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
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0008—Compounding the ingredient
- C06B21/0025—Compounding the ingredient the ingredient being a polymer bonded explosive or thermic component
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/18—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component
- C06B45/20—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an organic explosive or an organic thermic component
- C06B45/22—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an organic explosive or an organic thermic component the coating containing an organic compound
-
- 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
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0033—Shaping the mixture
- C06B21/0041—Shaping the mixture by compression
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0083—Treatment of solid structures, e.g. for coating or impregnating with a modifier
-
- 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
- C06B25/18—Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition
- C06B25/20—Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition with a non-explosive or a non-explosive or a non-thermic component
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- 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
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
- C06B47/14—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase comprising a solid component and an aqueous phase
- C06B47/145—Water in oil emulsion type explosives in which a carbonaceous fuel forms the continuous phase
Definitions
- the present invention relates to a press polymer-bonded explosive and, more particularly, to a method of manufacturing a press polymer-bonded explosive, in which a polymer emulsion is used to maximize the efficiency of a process, and a press polymer-bonded explosive manufactured using the same.
- a press polymer-bonded explosive (hereinafter, also referred to as pressable polymer-bonded explosive or Press-PBXs or P-PBXs) is a granular powder polymer-bonded explosive manufactured by adding a solvent, containing a polymer binder dissolved therein, to a suspension in which explosive particles are dispersed in water, thus agglomerating the explosive particles and the polymer binder.
- the press polymer-bonded explosive is compression molded to be used as a main charge or a booster charge for a weapon system.
- the press polymer-bonded explosive is mainly applied to ammunition and warheads which require the fragmentation performance and the jet performance of a shaped charge, because the content ratio of the explosive particles is the highest.
- a press polymer-bonded explosive is manufactured by applying a water-slurry (hereinafter, also referred to as WS) process.
- the WS process includes adding a coating solution, in which a plasticizer and a polymer binder are dissolved in an organic solvent, to a suspension, in which raw materials containing explosive particles are dispersed and agitated in water at a temperature of about 60°C, to thus perform coating and agglomeration of the raw materials, and then removing the organic solvent using distillation at a high temperature of about 100°C or more, thereby ultimately obtaining a granular powder (molding powder) of a press polymer-bonded explosive.
- a coating solution in which a plasticizer and a polymer binder are dissolved in an organic solvent
- the WS process is disadvantageous in that a distillation process at a high temperature of 100°C or more is inevitable for removing the organic solvent after coating and agglomeration of the raw materials. Moreover, there is a danger in terms of handling safety of the organic solvent, as well as the problem of environmental harm.
- US 2006/060273 A1 describes a method of preparing low-sensitivity, pressable aluminum-containing explosive compositions, in which polymer binder in an organic ethyl acetate solution is used.
- US 2005/072503 A1 describes pressable explosive compositions with enhanced sensitivity characteristics and processability. Therein, a solution of a binder Hy Temp dissolved in an organic ethyl acetate solution is used and a distillation step is required.
- FR 2 031 677 A5 describes a method of mixing with agitation crystals of an explosive material with a finely divided metal and a bonding agent in the liquid state in water with or without a solvent, fixing the bonding agent by cooling, distillation, or coagulation, and recovering a powder comprising explosive material and metal embedded in the bonding agent.
- the present invention has been made keeping in mind the above problems encountered in the related art, and it is an object of the present invention to provide a method of manufacturing a press polymer-bonded explosive according to claim 1, in which a polymer emulsion is used instead of an organic solvent to maximize the efficiency of a process, and a press polymer bonded explosive according to claim 8.
- the present invention provides a method as defined in claim 1.
- the emulsifier is one or more among sodium dodecyl sulfonate (SDS), sodium dodecyl benzene sulfonate (SDBS), sodium dioctyl sulfosuccinate, acetyl dimethyl benzyl ammonium chloride, and hexadecyl trimethyl ammonium bromide.
- SDS sodium dodecyl sulfonate
- SDBS sodium dodecyl benzene sulfonate
- sodium dioctyl sulfosuccinate sodium dioctyl sulfosuccinate
- acetyl dimethyl benzyl ammonium chloride and hexadecyl trimethyl ammonium bromide.
- the emulsifier is added in an amount of 0.1 to 5 wt% based on a weight of the process water.
- the explosive is one or more among trimethylenetrinitroamine (RDX), tetramethylenetetranitroamine (HMX), and hexanitrohexaazaisowurtzitane (HNIW), and is dispersed in an amount of 5 to 30 wt% based on a weight of the process water.
- RDX trimethylenetrinitroamine
- HMX tetramethylenetetranitroamine
- HNIW hexanitrohexaazaisowurtzitane
- the emulsion breaker is one or more among calcium chloride (calcium dichloride), sodium chloride, potassium chloride, magnesium chloride, sodium nitrate, sodium carbonate, sodium iodide, and potassium iodide as an inorganic salt.
- calcium chloride calcium dichloride
- sodium chloride sodium chloride
- potassium chloride magnesium chloride
- sodium nitrate sodium carbonate
- sodium iodide sodium iodide
- potassium iodide potassium iodide as an inorganic salt.
- the raw material further includes one or more metals among aluminum, magnesium, and boron.
- the plasticizer is one or more among dioctyl adipate (DOA), dioctyl sebacate, dioctyl phthalate (DOP), and isododecyl pelargonate (IDP).
- DOA dioctyl adipate
- DOP dioctyl phthalate
- IDP isododecyl pelargonate
- a press polymer-bonded explosive of the present invention is defined in claim 8.
- the process of distilling the organic solvent is not required, there is no need to allocate dead volume in a reactor, which corresponds to about 1/2 of the total volume of the reactor, to prevent the slurry from overflowing when the organic solvent is distilled. Therefore, the production amount per reactor is increased by about 200%. As a result, the production amount per unit time and per reactor is increased by about 1000%.
- energy metal particles (aluminum, magnesium, and boron), which have not been used as the composition of the polymer-bonded explosive due to a hydration reaction with water at a high distillation temperature, are capable of being used, it is possible to greatly improve the explosion energy of the press polymer-bonded explosive that is ultimately manufactured.
- FIG. 1 is a mimetic diagram showing a conventional method of manufacturing a press polymer-bonded explosive.
- the press polymer-bonded explosive is manufactured according to a WS (water-slurry) process using a coating solution manufactured by mixing a polymer binder and a plasticizer with an organic solvent.
- the WS process is disadvantageous in that a distillation process at a high temperature of 100°C or more is inevitable for removing the organic solvent after coating and agglomeration of raw materials.
- the use of metal particles, which contribute to improvement of the explosion energy of the polymer-bonded explosive is limited because the hydration reaction of metal is accelerated at high temperatures.
- the present invention is directed to solve the above-described problems, and relates to a method of manufacturing a press polymer-bonded explosive, in which a polymer emulsion is used instead of an organic solvent to maximize the efficiency of a process, and a press polymer-bonded explosive manufactured using the same.
- FIG. 2 is a flowchart showing a method of manufacturing a press polymer-bonded explosive according to the present invention
- FIG. 3 is a mimetic diagram showing the method of manufacturing the press polymer-bonded explosive according to the present invention.
- the present invention will be described with reference to FIGS. 2 and 3 .
- the present invention includes, in sequence, a polymer-emulsion-manufacturing step of adding a monomer of a polymer binder and an emulsifier to process water, mixing them, and then adding an initiator to thus manufacture a polymer emulsion using a polymerization reaction (S1 10), a slurry-manufacturing step of dispersing a raw material including an explosive and an emulsion breaker in fresh process water to thus manufacture a slurry (S 120), an agglomerated-particle-forming step of adding the manufactured polymer emulsion to the manufactured slurry to thus form agglomerated particles in which the surface of the raw material is coated with the polymer binder (S130), and an agglomerated-particle-obtaining step of collecting the agglomerated particles using filtration and drying the collected agglomerated particles (S140).
- a polymer-emulsion-manufacturing step of adding a monomer of a polymer binder and an emul
- the present invention further includes, after the agglomerated-particle-forming step (S130), a process-water-exchanging step of filtering the slurry, in which the agglomerated particles are formed, to thus collect the agglomerated particles and re-dispersing the collected agglomerated particles in new process water (S131), and a plasticizer addition step of adding a plasticizer and performing mixing (S 132).
- the polymer-emulsion-manufacturing step (S 110) is a step of manufacturing a water-based polymer emulsion in which the polymer binder is surrounded by the emulsifier in the process water.
- the emulsifier at a critical micelle concentration (CMC) or higher and the monomer of the polymer binder are added to the process water, followed by mixing, thus arranging the emulsifier to form a micelle structure.
- the monomer of the polymer binder is present in the micelle.
- the initiator is added to thus cause a polymerization reaction of the monomer, and the polymer binder is formed using the polymerization reaction.
- the water-based polymer emulsion in which the polymer binder is surrounded by the emulsifier in the process water is ultimately manufactured.
- the polymer binder is applied on the surface of the explosive particle during the agglomerated-particle-forming step (S130).
- the polymer binder is formed using the polymerization reaction of the monomer, and is one or more among a styrene butadiene rubber (SBR), neoprene, a nitrile butadiene rubber (NBR), an acrylic rubber, a fluorine-based rubber, and polyisobutylene.
- SBR styrene butadiene rubber
- NBR nitrile butadiene rubber
- acrylic rubber a fluorine-based rubber
- polyisobutylene polyisobutylene
- the monomer of the polymer binder is a monomer which forms one or more polymer binders among a styrene butadiene rubber (SBR), neoprene, a nitrile butadiene rubber (NBR), an acrylic rubber, a fluorine-based rubber, and polyisobutylene using the polymerization reaction. It is preferable to add the monomer of the polymer binder in an amount of 10 to 50 wt% based on the weight of the process water.
- SBR styrene butadiene rubber
- NBR nitrile butadiene rubber
- acrylic rubber a fluorine-based rubber
- polyisobutylene polyisobutylene
- the emulsifier is added in order to manufacture the polymer emulsion in which the polymer binder is surrounded by the emulsifier.
- the emulsifier is one or more among an anionic emulsifier, including sodium dodecyl sulfonate (SDS), sodium dodecyl benzene sulfonate (SDBS), and sodium dioctyl sulfosuccinate, and a cationic emulsifier, including acetyl dimethyl benzyl ammonium chloride and hexadecyl trimethyl ammonium bromide.
- SDS sodium dodecyl sulfonate
- SDBS sodium dodecyl benzene sulfonate
- a cationic emulsifier including acetyl dimethyl benzyl ammonium chloride and hexadecyl trimethyl ammonium bromide.
- the emulsifier in an amount of 0.1 to 5 wt% based on the weight of the process water.
- the reason for this is based on the following.
- the amount of the emulsifier is less than 0.1 wt%, since a micelle structure is not formed, the monomer of the polymer binder cannot be polymerized. As a result, the polymer emulsion is not manufactured.
- the amount of the emulsifier is more than 5 wt%, the emulsifier is expressed in a complicated nanostructure rather than a micelle structure, which hinders the formation of a spherical polymer emulsion.
- the initiator is added to initiate the polymerization reaction of the monomer, and is preferably one or more among potassium persulfate, sodium persulfate, ammonium persulfate, and hydrogen peroxide, but is not particularly limited thereto.
- a cross-linking agent such as divinyl benzene (DVB) or a chain transfer agent such as tetra-dodecylmercaptan (tert-dodecylmercaptan) may be added during the polymerization reaction, and the amount thereof is preferably less than 1 % of the molar ratio of the monomer of the polymer binder.
- a cross-linking agent such as divinyl benzene (DVB) or a chain transfer agent such as tetra-dodecylmercaptan (tert-dodecylmercaptan)
- tert-dodecylmercaptan tetra-dodecylmercaptan
- the slurry-manufacturing step (S 120) is a step of manufacturing a slurry in which an explosive is dispersed, and the raw material containing the explosive is added to the process water and then sufficiently dispersed, thus manufacturing the slurry.
- the explosive is preferably one or more among trimethylenetrinitroamine (RDX), tetramethylenetetranitroamine (HMX), and hexanitrohexaazaisowurtzitane (HNIW), and is preferably added in an amount of 5 to 30 wt% based on the weight of the process water.
- RDX trimethylenetrinitroamine
- HMX tetramethylenetetranitroamine
- HNIW hexanitrohexaazaisowurtzitane
- the reason for this is based on the following.
- the amount of the explosive is less than 5 wt%, since the amount (yield) of the ultimately obtained agglomerated particles is very small, the efficiency of the process is reduced.
- the amount of the explosive is more than 30 wt%, since the concentration of the slurry is high, it is difficult to sufficiently disperse the raw material in the process water, so great agglomeration of the explosive particles may occur.
- the explosive and a metal in a powder state may be further included in the raw material, and the metal is preferably one or more among aluminum, magnesium, and boron, which are energy metals capable of improving the explosion performance of the press polymer-bonded explosive that is ultimately manufactured.
- the slurry is manufactured by mixing a raw material (an explosive or an explosive and a metal) and an emulsion breaker (or a demulsifier), and the emulsion breaker serves to precipitate the polymer binder emulsified by the emulsifier in the polymer emulsion that is added during the agglomerated-particle-forming step (S130).
- a raw material an explosive or an explosive and a metal
- an emulsion breaker or a demulsifier
- the emulsion breaker is preferably one or more among calcium chloride (calcium dichloride, CaCl 2 ), sodium chloride (NaCl), potassium chloride (KCl), magnesium chloride (MgCl 2 ), sodium nitrate (NaNO 3 ), sodium carbonate (NaCO 3 ), sodium iodide (NaI), and potassium iodide (KI) as an inorganic salt.
- the emulsion breaker is sufficiently added in such an amount as to be able to precipitate the entire amount of the polymer binder emulsified in the polymer emulsion added during the agglomerated-particle-forming step (S130). More specifically, the emulsion breaker may be added in an amount equal to or greater than the weight of the polymer binder contained in the polymer emulsion.
- the reason for this is that, when the polymer binder that is not be precipitated is present in a large amount, a raw material (an explosive or an explosive and a metal) that is not coated with the polymer binder may be present.
- the emulsion breaker has no effect on the manufacturing process because it is removed during the process-water-exchanging step (S131), even when a large amount of the emulsion breaker has been added.
- a dispersant such as IPA (isopropyl alcohol) may be added, or a dispersing device such as a sonicator may be used for a predetermined time, so that a raw material (an explosive or an explosive and a metal) is sufficiently dispersed in the process water.
- IPA isopropyl alcohol
- the slurry-manufacturing step (S120) is preferably performed at room temperature. More specifically, the slurry-manufacturing step (S120) is preferably performed at a temperature of 20 to 40°C.
- the agglomerated-particle-forming step (S130) is a step of forming agglomerated particles in which the surface of the raw material, that is, the explosive or the explosive and the metal, is coated with the polymer binder and agglomerated therewith.
- the polymer emulsion manufactured during the polymer-emulsion-manufacturing step (S110) is added in a predetermined amount to the slurry manufactured during the slurry-manufacturing step (S120) and is agitated.
- the agglomerated-particle-forming step is preferably performed at room temperature. More specifically, the agglomerated-particle-forming step is preferably performed at a temperature of 20 to 40°C.
- the polymer emulsion containing the polymer binder emulsified by the emulsifier is added to the slurry containing the raw material (the explosive or the explosive and the metal) and the emulsion breaker, the polymer binder emulsified by the emulsifier is precipitated due to the emulsion breaker, and the precipitated polymer binder is applied on the surface of the explosive or the explosive and the metal and agglomerated therewith, thus forming the agglomerated particles.
- the weight of the polymer emulsion added to the slurry is preferably adjusted depending on the chemical composition of the agglomerated particles ultimately obtained during the subsequent agglomerated-particle-obtaining step (S140). More specifically, it is preferable to determine the addition amount depending on the weight percentage of the polymer binder, which is to be included, based on the total weight of the agglomerated particles that are ultimately obtained.
- the agglomerated particles manufactured using the manufacturing method of the present invention preferably include 50 to 98 wt% of the explosive, 0 to 40 wt% of the metal, and 0.5 to 5 wt% of the polymer binder based on the total weight of agglomerated particles.
- the reason for this is based on the following.
- the amount of the polymer binder is less than 0.5 wt%, since explosive particles that are not coated with the polymer binder and not agglomerated are present in a large amount, they may be susceptible to unexpected external stimuli such as heat and impact.
- the amount of the polymer binder is more than 5 wt%, the physical properties of the polymer-bonded explosive may be reduced.
- the weight of the polymer emulsion added to the slurry during the agglomerated-particle-forming step (S130) is calculated so that the agglomerated particles ultimately obtained include 0.5 to 5 wt% of the polymer binder based on the total weight of agglomerated particles, in consideration of the weights of the explosive and the metal used during the manufacture of the slurry (S120) and the weight of the polymer binder precipitated by the emulsion breaker, and the polymer emulsion is then added.
- the slurry may be aged for a predetermined time after the agglomerated particles are formed, thus adjusting the size and the shape of the agglomerated particles.
- the agglomerated particles are coated with the polymer binder and are agglomerated to gradually grow.
- the aging time may be about 10 minutes or more, but is not limited thereto, and may be adjusted depending on the desired size and shape of the agglomerated particles.
- a process-water-exchanging step (S131) is performed, in which the slurry having the agglomerated particles formed therein is filtered using a filtration apparatus to thus collect the agglomerated particles and the collected agglomerated particles are added again to new process water.
- residues such as inorganic salts formed by the emulsifier and the emulsion breaker remaining in the slurry may be removed, so that the agglomerated particles ultimately obtained during the agglomerated-particle-obtaining step (S140) can be free from impurities.
- a plasticizer addition step (S132) is performed, in which a plasticizer is added to the process water containing the agglomerated particles added again thereto and is then mixed so that the plasticizer is agglomerated with the agglomerated particles.
- the plasticizer is preferably one or more among dioctyl adipate (DOA), dioctyl sebacate, dioctyl phthalate (DOP), and isododecyl pelargonate (IDP).
- the weight of the added plasticizer is preferably adjusted depending on the chemical composition of the agglomerated particles ultimately obtained during the subsequent agglomerated-particle-obtaining step (S140). More specifically, it is preferable to determine the addition amount depending on the weight percentage of the plasticizer, which is to be included, based on the total weight of the agglomerated particles that is ultimately obtained.
- the agglomerated particles manufactured using the manufacturing method of the present invention preferably include 50 to 98 wt% of the explosive, 0 to 40 wt% of the metal, 0.5 to 5 wt% of the polymer binder, and 0 to 10 wt% of the plasticizer based on the total weight of agglomerated particles.
- the reason for this is that when the amount of the plasticizer is more than 10 wt%, the physical properties of the polymer-bonded explosive may be deteriorated.
- the weight of the plasticizer added during the plasticizer addition step (S132) is calculated so that the agglomerated particles ultimately obtained include 0 to 10 wt% of the plasticizer based on the total weight of agglomerated particles, in consideration of the weights of the explosive and the metal used during the manufacture of the slurry (S120), and the plasticizer is then added.
- filtration is performed using a filtration apparatus to thus collect the agglomerated particles, and the collected agglomerated particles are placed in an oven capable of circulating air and are dried so as to have a water content of about 0.5% or less, thereby obtaining final agglomerated particles (S140).
- the agglomerated particles that are ultimately obtained include 50 to 98 wt% of the explosive, 0 to 40 wt% of the metal, 0.5 to 5 wt% of the polymer binder, and 0 to 10 wt% of the plasticizer based on the total weight of agglomerated particles.
- the agglomerated particles are compression molded, thus manufacturing a press polymer-bonded explosive.
- the press polymer-bonded explosive manufactured according to the present invention has the same chemical composition as the chemical composition of the agglomerated particles.
- the manufactured coating solution was added to the manufactured slurry to thus form agglomerated particles. Then, aging was performed for about 10 minutes, enabling the agglomerated particles to grow. Thereafter, 3120 g of the process water was added, thus terminating the growth of the agglomerated particles. After heating to about 100°C, the temperature was maintained for about 30 to 50 minutes, thus removing the organic solvent by distillation. Thereafter, 1300 g of agglomerated particles was ultimately obtained using filtration and drying processes.
- Table 1 shows the result obtained by confirming the composition using a weight difference before and after extraction, after the agglomerated particles manufactured in the Example are dissolved in hexane, which is a solvent for dissolving dioctyl adipate, which is the plasticizer, and in acetone, which is a solvent for dissolving RDX, which is the explosive, followed by extraction.
- hexane which is a solvent for dissolving dioctyl adipate, which is the plasticizer
- acetone which is a solvent for dissolving RDX, which is the explosive
- Table 2 shows the results of the sensitivity tests of impact, friction, static electricity, and shock of the agglomerated particles manufactured in the Comparative Example and the Example.
- FIGS. 4 and 5 show the SEM results of the agglomerated particles manufactured using the conventional method of manufacturing the press polymer-bonded explosive
- FIGS. 6 and 7 show the SEM results of the agglomerated particles manufactured using the method of manufacturing the press polymer-bonded explosive according to the present invention.
- the weight was allowed to free-fall while the weight and height thereof were changed to measure the energy when an explosion reaction of a sample occurred with a probability of 50%.
- the weight of the weight provided on the equidistant groove formed in a long lever and the position of the equidistant groove were changed to measure the energy when the explosion reaction of a sample fastened to the front bottom of the long lever occurred at a probability of 50%.
- electrical energy was applied to measure whether or not the sample reacted.
- an attenuator (gap) was placed between a shock pressure source (a donor explosive) and the sample, and the shock pressure source was detonated to measure the thickness of the attenuator when the explosion reaction of the sample occurred with a probability of 50%.
- the impact sensitivity, friction sensitivity, static-electricity sensitivity, shock sensitivity and shape of the agglomerated particles manufactured according to the manufacturing method of the present invention are almost the same as those of the agglomerated particles manufactured according to a conventional manufacturing method using an organic solvent.
- This result shows that the manufacturing method of the present invention has the excellent efficiency of a process from the aspects of time, costs, and production amounts (agglomerated particles weighing about three times or more are obtained based on the same volume of reactor (25 liters)) and that even the agglomerated particles having the same characteristics can be manufactured.
- the polymer emulsion is used instead of the organic solvent, which maximizes the efficiency of a process from the aspects of time, costs, and production amounts. Moreover, since an organic solvent is not used, safety and eco-friendliness of the process are secured.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
- The present invention relates to a press polymer-bonded explosive and, more particularly, to a method of manufacturing a press polymer-bonded explosive, in which a polymer emulsion is used to maximize the efficiency of a process, and a press polymer-bonded explosive manufactured using the same.
- Explosions of explosives cause extensive loss of life and tremendous property damage once they occur because there is no time to evacuate. For this reason, there has been a need for an insensitive explosive, which is an explosive not causing an explosion reaction in response to unexpected external stimuli such as heat and shocks, and the demand thereof has also increased. Therefore, studies have been made on the manufacture of a polymer-bonded explosive in which a raw material explosive is desensitized or in which explosive particles are coated with a polymer binder to reduce sensitivity.
- Of the various types of polymer-bonded explosives, a press polymer-bonded explosive (hereinafter, also referred to as pressable polymer-bonded explosive or Press-PBXs or P-PBXs) is a granular powder polymer-bonded explosive manufactured by adding a solvent, containing a polymer binder dissolved therein, to a suspension in which explosive particles are dispersed in water, thus agglomerating the explosive particles and the polymer binder. The press polymer-bonded explosive is compression molded to be used as a main charge or a booster charge for a weapon system. Moreover, the press polymer-bonded explosive is mainly applied to ammunition and warheads which require the fragmentation performance and the jet performance of a shaped charge, because the content ratio of the explosive particles is the highest.
- Generally, such a press polymer-bonded explosive is manufactured by applying a water-slurry (hereinafter, also referred to as WS) process. The WS process includes adding a coating solution, in which a plasticizer and a polymer binder are dissolved in an organic solvent, to a suspension, in which raw materials containing explosive particles are dispersed and agitated in water at a temperature of about 60°C, to thus perform coating and agglomeration of the raw materials, and then removing the organic solvent using distillation at a high temperature of about 100°C or more, thereby ultimately obtaining a granular powder (molding powder) of a press polymer-bonded explosive.
- However, the WS process is disadvantageous in that a distillation process at a high temperature of 100°C or more is inevitable for removing the organic solvent after coating and agglomeration of the raw materials. Moreover, there is a danger in terms of handling safety of the organic solvent, as well as the problem of environmental harm.
-
US 2006/060273 A1 describes a method of preparing low-sensitivity, pressable aluminum-containing explosive compositions, in which polymer binder in an organic ethyl acetate solution is used. -
US 2005/072503 A1 describes pressable explosive compositions with enhanced sensitivity characteristics and processability. Therein, a solution of a binder Hy Temp dissolved in an organic ethyl acetate solution is used and a distillation step is required. -
FR 2 031 677 A5 - The above-mentioned background arts are intended to aid understanding of the background of the invention, and may include matters other than conventional technologies previously known to those skilled in the art.
- Accordingly, the present invention has been made keeping in mind the above problems encountered in the related art, and it is an object of the present invention to provide a method of manufacturing a press polymer-bonded explosive according to
claim 1, in which a polymer emulsion is used instead of an organic solvent to maximize the efficiency of a process, and a press polymer bonded explosive according to claim 8. - In order to accomplish the above object, the present invention provides a method as defined in
claim 1. - Preferably, during the polymer-emulsion-manufacturing step (S110), the emulsifier is one or more among sodium dodecyl sulfonate (SDS), sodium dodecyl benzene sulfonate (SDBS), sodium dioctyl sulfosuccinate, acetyl dimethyl benzyl ammonium chloride, and hexadecyl trimethyl ammonium bromide.
- Preferably, during the polymer-emulsion-manufacturing step (S110), the emulsifier is added in an amount of 0.1 to 5 wt% based on a weight of the process water.
- Preferably, during the slurry-manufacturing step (S120), the explosive is one or more among trimethylenetrinitroamine (RDX), tetramethylenetetranitroamine (HMX), and hexanitrohexaazaisowurtzitane (HNIW), and is dispersed in an amount of 5 to 30 wt% based on a weight of the process water.
- Preferably, during the slurry-manufacturing step (S120), the emulsion breaker is one or more among calcium chloride (calcium dichloride), sodium chloride, potassium chloride, magnesium chloride, sodium nitrate, sodium carbonate, sodium iodide, and potassium iodide as an inorganic salt.
- Preferably, during the slurry-manufacturing step (S120), the raw material further includes one or more metals among aluminum, magnesium, and boron.
- Preferably, during the plasticizer addition step (S132), the plasticizer is one or more among dioctyl adipate (DOA), dioctyl sebacate, dioctyl phthalate (DOP), and isododecyl pelargonate (IDP).
- In addition, a press polymer-bonded explosive of the present invention is defined in claim 8.
- In the present invention, since a polymer emulsion is used instead of an organic solvent, a distillation process at a high temperature of 100°C or more is not required. Accordingly, the manufacturing time is shortened to thus reduce costs, thereby maximizing the efficiency of the process.
- Further, since the process of distilling the organic solvent is not required, there is no need to allocate dead volume in a reactor, which corresponds to about 1/2 of the total volume of the reactor, to prevent the slurry from overflowing when the organic solvent is distilled. Therefore, the production amount per reactor is increased by about 200%. As a result, the production amount per unit time and per reactor is increased by about 1000%.
- Moreover, since an organic solvent is not used, safety and eco-friendliness of the process are high.
- In addition, since energy metal particles (aluminum, magnesium, and boron), which have not been used as the composition of the polymer-bonded explosive due to a hydration reaction with water at a high distillation temperature, are capable of being used, it is possible to greatly improve the explosion energy of the press polymer-bonded explosive that is ultimately manufactured.
-
-
FIG. 1 is a mimetic diagram showing a conventional method of manufacturing a press polymer-bonded explosive; -
FIG. 2 is a flowchart showing a method of manufacturing a press polymer-bonded explosive according to the present invention; -
FIG. 3 is a mimetic diagram showing the method of manufacturing the press polymer-bonded explosive according to the present invention; -
FIGS. 4 and5 show the SEM results of agglomerated particles manufactured using the conventional method of manufacturing the press polymer-bonded explosive; and -
FIGS. 6 and7 show the SEM results of agglomerated particles manufactured using the method of manufacturing the press polymer-bonded explosive according to the present invention. - The technical terms used in the present specification should be interpreted in a sense generally understood by those skilled in the art to which the present invention belongs, and should not be construed in an overly broad sense or an overly narrow sense, unless defined otherwise in the present invention. In addition, the general terms used in the present invention should be interpreted according to definitions in a dictionary or according to the context.
- Further, the singular forms used in the present specification include plural referents unless the context clearly dictates otherwise. That is, the terms 'constituting', 'comprising', or 'including', as used herein, should not be construed as necessarily including the various elements or steps described in the specification, but it is to be understood that some components or some steps may not be included, or that additional components or steps may be included therein.
-
FIG. 1 is a mimetic diagram showing a conventional method of manufacturing a press polymer-bonded explosive. As shown inFIG. 1 , the press polymer-bonded explosive is manufactured according to a WS (water-slurry) process using a coating solution manufactured by mixing a polymer binder and a plasticizer with an organic solvent. However, the WS process is disadvantageous in that a distillation process at a high temperature of 100°C or more is inevitable for removing the organic solvent after coating and agglomeration of raw materials. Moreover, there is a danger in terms of handling safety of the organic solvent, as well as the problem of environmental harm. Further, the use of metal particles, which contribute to improvement of the explosion energy of the polymer-bonded explosive, is limited because the hydration reaction of metal is accelerated at high temperatures. - Accordingly, the present invention is directed to solve the above-described problems, and relates to a method of manufacturing a press polymer-bonded explosive, in which a polymer emulsion is used instead of an organic solvent to maximize the efficiency of a process, and a press polymer-bonded explosive manufactured using the same.
-
FIG. 2 is a flowchart showing a method of manufacturing a press polymer-bonded explosive according to the present invention, andFIG. 3 is a mimetic diagram showing the method of manufacturing the press polymer-bonded explosive according to the present invention. Hereinafter, the present invention will be described with reference toFIGS. 2 and3 . - As shown in
FIG. 2 , the present invention includes, in sequence, a polymer-emulsion-manufacturing step of adding a monomer of a polymer binder and an emulsifier to process water, mixing them, and then adding an initiator to thus manufacture a polymer emulsion using a polymerization reaction (S1 10), a slurry-manufacturing step of dispersing a raw material including an explosive and an emulsion breaker in fresh process water to thus manufacture a slurry (S 120), an agglomerated-particle-forming step of adding the manufactured polymer emulsion to the manufactured slurry to thus form agglomerated particles in which the surface of the raw material is coated with the polymer binder (S130), and an agglomerated-particle-obtaining step of collecting the agglomerated particles using filtration and drying the collected agglomerated particles (S140). - In addition, the present invention further includes, after the agglomerated-particle-forming step (S130), a process-water-exchanging step of filtering the slurry, in which the agglomerated particles are formed, to thus collect the agglomerated particles and re-dispersing the collected agglomerated particles in new process water (S131), and a plasticizer addition step of adding a plasticizer and performing mixing (S 132).
- Hereinafter, each step will be described in more detail.
- The polymer-emulsion-manufacturing step (S 110) is a step of manufacturing a water-based polymer emulsion in which the polymer binder is surrounded by the emulsifier in the process water. In this step, first, the emulsifier at a critical micelle concentration (CMC) or higher and the monomer of the polymer binder are added to the process water, followed by mixing, thus arranging the emulsifier to form a micelle structure. The monomer of the polymer binder is present in the micelle.
- Thereafter, the initiator is added to thus cause a polymerization reaction of the monomer, and the polymer binder is formed using the polymerization reaction. In addition, the water-based polymer emulsion in which the polymer binder is surrounded by the emulsifier in the process water is ultimately manufactured.
- The polymer binder is applied on the surface of the explosive particle during the agglomerated-particle-forming step (S130). As described above, the polymer binder is formed using the polymerization reaction of the monomer, and is one or more among a styrene butadiene rubber (SBR), neoprene, a nitrile butadiene rubber (NBR), an acrylic rubber, a fluorine-based rubber, and polyisobutylene.
- Accordingly, the monomer of the polymer binder is a monomer which forms one or more polymer binders among a styrene butadiene rubber (SBR), neoprene, a nitrile butadiene rubber (NBR), an acrylic rubber, a fluorine-based rubber, and polyisobutylene using the polymerization reaction. It is preferable to add the monomer of the polymer binder in an amount of 10 to 50 wt% based on the weight of the process water.
- In addition, the emulsifier is added in order to manufacture the polymer emulsion in which the polymer binder is surrounded by the emulsifier. Preferably, the emulsifier is one or more among an anionic emulsifier, including sodium dodecyl sulfonate (SDS), sodium dodecyl benzene sulfonate (SDBS), and sodium dioctyl sulfosuccinate, and a cationic emulsifier, including acetyl dimethyl benzyl ammonium chloride and hexadecyl trimethyl ammonium bromide.
- It is preferable to add the emulsifier in an amount of 0.1 to 5 wt% based on the weight of the process water. The reason for this is based on the following. When the amount of the emulsifier is less than 0.1 wt%, since a micelle structure is not formed, the monomer of the polymer binder cannot be polymerized. As a result, the polymer emulsion is not manufactured. When the amount of the emulsifier is more than 5 wt%, the emulsifier is expressed in a complicated nanostructure rather than a micelle structure, which hinders the formation of a spherical polymer emulsion.
- The initiator is added to initiate the polymerization reaction of the monomer, and is preferably one or more among potassium persulfate, sodium persulfate, ammonium persulfate, and hydrogen peroxide, but is not particularly limited thereto.
- In addition to the initiator, a cross-linking agent such as divinyl benzene (DVB) or a chain transfer agent such as tetra-dodecylmercaptan (tert-dodecylmercaptan) may be added during the polymerization reaction, and the amount thereof is preferably less than 1 % of the molar ratio of the monomer of the polymer binder.
- The slurry-manufacturing step (S 120) is a step of manufacturing a slurry in which an explosive is dispersed, and the raw material containing the explosive is added to the process water and then sufficiently dispersed, thus manufacturing the slurry.
- The explosive is preferably one or more among trimethylenetrinitroamine (RDX), tetramethylenetetranitroamine (HMX), and hexanitrohexaazaisowurtzitane (HNIW), and is preferably added in an amount of 5 to 30 wt% based on the weight of the process water.
- The reason for this is based on the following. When the amount of the explosive is less than 5 wt%, since the amount (yield) of the ultimately obtained agglomerated particles is very small, the efficiency of the process is reduced. When the amount of the explosive is more than 30 wt%, since the concentration of the slurry is high, it is difficult to sufficiently disperse the raw material in the process water, so great agglomeration of the explosive particles may occur.
- Meanwhile, the explosive and a metal in a powder state may be further included in the raw material, and the metal is preferably one or more among aluminum, magnesium, and boron, which are energy metals capable of improving the explosion performance of the press polymer-bonded explosive that is ultimately manufactured.
- In addition, the slurry is manufactured by mixing a raw material (an explosive or an explosive and a metal) and an emulsion breaker (or a demulsifier), and the emulsion breaker serves to precipitate the polymer binder emulsified by the emulsifier in the polymer emulsion that is added during the agglomerated-particle-forming step (S130).
- The emulsion breaker is preferably one or more among calcium chloride (calcium dichloride, CaCl2), sodium chloride (NaCl), potassium chloride (KCl), magnesium chloride (MgCl2), sodium nitrate (NaNO3), sodium carbonate (NaCO3), sodium iodide (NaI), and potassium iodide (KI) as an inorganic salt.
- In addition, preferably, the emulsion breaker is sufficiently added in such an amount as to be able to precipitate the entire amount of the polymer binder emulsified in the polymer emulsion added during the agglomerated-particle-forming step (S130). More specifically, the emulsion breaker may be added in an amount equal to or greater than the weight of the polymer binder contained in the polymer emulsion.
- The reason for this is that, when the polymer binder that is not be precipitated is present in a large amount, a raw material (an explosive or an explosive and a metal) that is not coated with the polymer binder may be present. In addition, the emulsion breaker has no effect on the manufacturing process because it is removed during the process-water-exchanging step (S131), even when a large amount of the emulsion breaker has been added.
- Meanwhile, during the slurry-manufacturing step (S120), a dispersant such as IPA (isopropyl alcohol) may be added, or a dispersing device such as a sonicator may be used for a predetermined time, so that a raw material (an explosive or an explosive and a metal) is sufficiently dispersed in the process water.
- Further, in consideration of the characteristics of the metal, which accelerates a hydration reaction with a heat-sensitive explosive at high temperatures, the slurry-manufacturing step (S120) is preferably performed at room temperature. More specifically, the slurry-manufacturing step (S120) is preferably performed at a temperature of 20 to 40°C.
- The agglomerated-particle-forming step (S130) is a step of forming agglomerated particles in which the surface of the raw material, that is, the explosive or the explosive and the metal, is coated with the polymer binder and agglomerated therewith. The polymer emulsion manufactured during the polymer-emulsion-manufacturing step (S110) is added in a predetermined amount to the slurry manufactured during the slurry-manufacturing step (S120) and is agitated. In consideration of the characteristics of the metal, which accelerates a hydration reaction with a heat-sensitive explosive at high temperatures, the agglomerated-particle-forming step is preferably performed at room temperature. More specifically, the agglomerated-particle-forming step is preferably performed at a temperature of 20 to 40°C.
- When the polymer emulsion containing the polymer binder emulsified by the emulsifier is added to the slurry containing the raw material (the explosive or the explosive and the metal) and the emulsion breaker, the polymer binder emulsified by the emulsifier is precipitated due to the emulsion breaker, and the precipitated polymer binder is applied on the surface of the explosive or the explosive and the metal and agglomerated therewith, thus forming the agglomerated particles.
- The weight of the polymer emulsion added to the slurry is preferably adjusted depending on the chemical composition of the agglomerated particles ultimately obtained during the subsequent agglomerated-particle-obtaining step (S140). More specifically, it is preferable to determine the addition amount depending on the weight percentage of the polymer binder, which is to be included, based on the total weight of the agglomerated particles that are ultimately obtained.
- In this connection, in the present invention, the agglomerated particles manufactured using the manufacturing method of the present invention preferably include 50 to 98 wt% of the explosive, 0 to 40 wt% of the metal, and 0.5 to 5 wt% of the polymer binder based on the total weight of agglomerated particles. The reason for this is based on the following. When the amount of the polymer binder is less than 0.5 wt%, since explosive particles that are not coated with the polymer binder and not agglomerated are present in a large amount, they may be susceptible to unexpected external stimuli such as heat and impact. When the amount of the polymer binder is more than 5 wt%, the physical properties of the polymer-bonded explosive may be reduced.
- Therefore, the weight of the polymer emulsion added to the slurry during the agglomerated-particle-forming step (S130) is calculated so that the agglomerated particles ultimately obtained include 0.5 to 5 wt% of the polymer binder based on the total weight of agglomerated particles, in consideration of the weights of the explosive and the metal used during the manufacture of the slurry (S120) and the weight of the polymer binder precipitated by the emulsion breaker, and the polymer emulsion is then added.
- Meanwhile, during the agglomerated-particle-forming step (S130), the slurry may be aged for a predetermined time after the agglomerated particles are formed, thus adjusting the size and the shape of the agglomerated particles. During the aging process, the agglomerated particles are coated with the polymer binder and are agglomerated to gradually grow. The aging time may be about 10 minutes or more, but is not limited thereto, and may be adjusted depending on the desired size and shape of the agglomerated particles.
- Meanwhile, after the agglomerated-particle-forming step (S130), a process-water-exchanging step (S131) is performed, in which the slurry having the agglomerated particles formed therein is filtered using a filtration apparatus to thus collect the agglomerated particles and the collected agglomerated particles are added again to new process water.
- Thereby, residues such as inorganic salts formed by the emulsifier and the emulsion breaker remaining in the slurry may be removed, so that the agglomerated particles ultimately obtained during the agglomerated-particle-obtaining step (S140) can be free from impurities.
- Meanwhile, after the process-water-exchanging step (S131), a plasticizer addition step (S132) is performed, in which a plasticizer is added to the process water containing the agglomerated particles added again thereto and is then mixed so that the plasticizer is agglomerated with the agglomerated particles. The plasticizer is preferably one or more among dioctyl adipate (DOA), dioctyl sebacate, dioctyl phthalate (DOP), and isododecyl pelargonate (IDP).
- The weight of the added plasticizer is preferably adjusted depending on the chemical composition of the agglomerated particles ultimately obtained during the subsequent agglomerated-particle-obtaining step (S140). More specifically, it is preferable to determine the addition amount depending on the weight percentage of the plasticizer, which is to be included, based on the total weight of the agglomerated particles that is ultimately obtained.
- In this connection, in the present invention, the agglomerated particles manufactured using the manufacturing method of the present invention preferably include 50 to 98 wt% of the explosive, 0 to 40 wt% of the metal, 0.5 to 5 wt% of the polymer binder, and 0 to 10 wt% of the plasticizer based on the total weight of agglomerated particles. The reason for this is that when the amount of the plasticizer is more than 10 wt%, the physical properties of the polymer-bonded explosive may be deteriorated.
- Therefore, the weight of the plasticizer added during the plasticizer addition step (S132) is calculated so that the agglomerated particles ultimately obtained include 0 to 10 wt% of the plasticizer based on the total weight of agglomerated particles, in consideration of the weights of the explosive and the metal used during the manufacture of the slurry (S120), and the plasticizer is then added.
- Meanwhile, after the plasticizer addition step (S132), filtration is performed using a filtration apparatus to thus collect the agglomerated particles, and the collected agglomerated particles are placed in an oven capable of circulating air and are dried so as to have a water content of about 0.5% or less, thereby obtaining final agglomerated particles (S140).
- The agglomerated particles that are ultimately obtained include 50 to 98 wt% of the explosive, 0 to 40 wt% of the metal, 0.5 to 5 wt% of the polymer binder, and 0 to 10 wt% of the plasticizer based on the total weight of agglomerated particles. The agglomerated particles are compression molded, thus manufacturing a press polymer-bonded explosive. In addition, the press polymer-bonded explosive manufactured according to the present invention has the same chemical composition as the chemical composition of the agglomerated particles.
- Hereinafter, the present invention will be described in more detail with reference to a Comparative Example and an Example. However, the following Comparative Example and Example are for illustrative purposes only and are not intended to limit the scope of the present invention.
- 26 g of an acrylic rubber (HYTEMP), which was a commercial polymer binder, and 78 g of dioctyl adipate (DOA), which was a plasticizer, were added to 520 g of ethyl acetate, which was an organic solvent, and were sufficiently dissolved at a temperature of 60°C for about 2 to 8 hours, thus manufacturing a coating solution. Thereafter, 1196 g of RDX (Hanwha Co., Ltd.) was added to 6500 g of a process water in a 25-liter reactor, and was agitated and dispersed at a temperature of 60°C for 10 minutes, thus manufacturing a slurry. Thereafter, the manufactured coating solution was added to the manufactured slurry to thus form agglomerated particles. Then, aging was performed for about 10 minutes, enabling the agglomerated particles to grow. Thereafter, 3120 g of the process water was added, thus terminating the growth of the agglomerated particles. After heating to about 100°C, the temperature was maintained for about 30 to 50 minutes, thus removing the organic solvent by distillation. Thereafter, 1300 g of agglomerated particles was ultimately obtained using filtration and drying processes.
- 1.24 g (0.0043 mol) of sodium dodecyl sulfonate, which was an emulsifier, 156 g (1.217 mol) of butyl acrylate, which was a monomer of a polymer binder, and 52 g (0.52 mol) of ethyl acrylate were added to 800 g of a process water on the basis of a 25-liter batch, and were agitated for 1 hour. Thereafter, 0.52 g (0.0019 mol) of potassium persulfate, which was an initiator, was added at a temperature of about 80 to 90°C, and a polymerization reaction was then performed at a temperature of 75°C for 5 to 10 hours, thus manufacturing a polymer emulsion (S1 10). Thereafter, 3600 g of RDX (Hanwha Co., Ltd.) and 80 g of calcium chloride (CaCl2), which was an emulsion breaker, were added to 20000 g of process water in a 25-liter reactor, and were agitated at a temperature of 25°C for 10 minutes, thus manufacturing a slurry. Thereafter, 400 g of the manufactured polymer emulsion (the amount of the included polymer binder was 80 g) was added to the manufactured slurry to thus form agglomerated particles. Then, aging was performed for about 10 minutes, enabling the agglomerated particles to grow. Thereafter, the agglomerated particles were collected by filtration, and the collected agglomerated particles were added again to new process water, thus removing the residue. Thereafter, 240 g of dioctyl adipate (DOA), which was a plasticizer, was added and agitated. Thereafter, 4000 g of agglomerated particles were ultimately obtained using filtration and drying processes.
[Table 1] Explosive (RDX) Polymer binder Plasticizer (DOA) Composition (wt%) 92.10 wt% 1.96 wt% 5.94 wt% - Table 1 shows the result obtained by confirming the composition using a weight difference before and after extraction, after the agglomerated particles manufactured in the Example are dissolved in hexane, which is a solvent for dissolving dioctyl adipate, which is the plasticizer, and in acetone, which is a solvent for dissolving RDX, which is the explosive, followed by extraction. The final residue after the extraction of dioctyl adipate and RDX has the composition of the polymer binder.
[Table 2] Manufacturing method Sensitivity Impact [J] Friction [Kg•f] Static electricity [J] Shock [kbar] Comparative Example 40.18 26.80 >25 38.16 sheets (150.38 kbar) Example 38.73 26.92 >25 37.90 sheets (151.88 kbar) - Table 2 shows the results of the sensitivity tests of impact, friction, static electricity, and shock of the agglomerated particles manufactured in the Comparative Example and the Example.
FIGS. 4 and5 show the SEM results of the agglomerated particles manufactured using the conventional method of manufacturing the press polymer-bonded explosive, andFIGS. 6 and7 show the SEM results of the agglomerated particles manufactured using the method of manufacturing the press polymer-bonded explosive according to the present invention. - In the impact sensitivity test, the weight was allowed to free-fall while the weight and height thereof were changed to measure the energy when an explosion reaction of a sample occurred with a probability of 50%. In the friction sensitivity test, the weight of the weight provided on the equidistant groove formed in a long lever and the position of the equidistant groove were changed to measure the energy when the explosion reaction of a sample fastened to the front bottom of the long lever occurred at a probability of 50%. In the static-electricity sensitivity test, electrical energy was applied to measure whether or not the sample reacted. In the shock sensitivity test, an attenuator (gap) was placed between a shock pressure source (a donor explosive) and the sample, and the shock pressure source was detonated to measure the thickness of the attenuator when the explosion reaction of the sample occurred with a probability of 50%.
- As seen from Table 2 and
FIG. 4 , the impact sensitivity, friction sensitivity, static-electricity sensitivity, shock sensitivity and shape of the agglomerated particles manufactured according to the manufacturing method of the present invention are almost the same as those of the agglomerated particles manufactured according to a conventional manufacturing method using an organic solvent. This result shows that the manufacturing method of the present invention has the excellent efficiency of a process from the aspects of time, costs, and production amounts (agglomerated particles weighing about three times or more are obtained based on the same volume of reactor (25 liters)) and that even the agglomerated particles having the same characteristics can be manufactured. - In the method of manufacturing the press polymer-bonded explosive using the polymer emulsion and the press polymer-bonded explosive manufactured using the same, which are the present invention, the polymer emulsion is used instead of the organic solvent, which maximizes the efficiency of a process from the aspects of time, costs, and production amounts. Moreover, since an organic solvent is not used, safety and eco-friendliness of the process are secured.
Claims (11)
- A method of manufacturing a compressed composite gunpowder using a polymer emulsion, the method comprising:a polymer-emulsion-manufacturing step of mixing a monomer of a polymer binder and an emulsifier with a process water and then adding an initiator to thus manufacture a polymer emulsion using a polymerization reaction;a slurry-manufacturing step of mixing a raw material including an explosive and an emulsion breaker with fresh process water to thus manufacture a slurry;an agglomerated-particle-forming step of adding the manufactured polymer emulsion to the manufactured slurry to thus form agglomerated particles in which a surface of the raw material is coated with the polymer binder;a process-water-exchanging step of collecting the agglomerated particles using filtration and adding again the collected agglomerated particles to a new process water;a plasticizer addition step of adding a plasticizer, thus agglomerating the agglomerated particles and the plasticizer; andan agglomerated-particle-obtaining step of collecting the agglomerated particles using filtration and drying the collected agglomerated particles,wherein during the polymer-emulsion-manufacturing step, the monomer forms the polymer binder of one or more among a styrene butadiene rubber (SBR), neoprene, a nitrile butadiene rubber (NBR), an acrylic rubber, a fluorine-based rubber, and polyisobutylene using the polymerization reaction.
- The method of claim 1, wherein during the polymer-emulsion-manufacturing step, the emulsifier is one or more among sodium dodecyl sulfonate (SDS), sodium dodecyl benzene sulfonate (SDBS), sodium dioctyl sulfosuccinate, acetyl dimethyl benzyl ammonium chloride, and hexadecyl trimethyl ammonium bromide.
- The method of claim 1, wherein during the polymer-emulsion-manufacturing step, the emulsifier is added in an amount of 0.1 to 5 wt% based on a weight of the process water.
- The method of claim 1, wherein during the slurry-manufacturing step, the explosive is one or more among trimethylenetrinitroamine (RDX), tetramethylenetetranitroamine (HMX), and hexanitrohexaazaisowurtzitane (HNIW), and is dispersed in an amount of 5 to 30 wt% based on a weight of the process water.
- The method of claim 1, wherein during the slurry-manufacturing step, the emulsion breaker is one or more among calcium chloride (calcium dichloride), sodium chloride, potassium chloride, magnesium chloride, sodium nitrate, sodium carbonate, sodium iodide, and potassium iodide as an inorganic salt.
- The method of claim 1, wherein during the slurry-manufacturing step, the raw material further includes one or more metals among aluminum, magnesium, and boron.
- The method of claim 1, wherein the plasticizer is one or more among dioctyl adipate (DOA), dioctyl sebacate, dioctyl phthalate (DOP), and isododecyl pelargonate (IDP).
- A compressed composite gunpowder comprising:50 to 98 wt% of an explosive;0 to 40 wt% of a metal;0.5 to 5 wt% of a polymer binder; and0 to 10 wt% of a plasticizer,wherein the polymer binder is one or more among a styrene butadiene rubber (SBR), neoprene, a nitrile butadiene rubber (NBR), a fluorine-based rubber, and polyisobutylene.
- The compressed composite gunpowder of claim 8, wherein the explosive is one or more among trimethylenetrinitroamine (RDX), tetramethylenetetranitroamine (HMX), and hexanitrohexaazaisowurtzitane (HNIW).
- The compressed composite gunpowder of claim 8, wherein the metal is one or more among aluminum, magnesium, and boron.
- The compressed composite gunpowder of claim 8, wherein the plasticizer is one or more among dioctyl adipate (DOA), dioctyl sebacate, dioctyl phthalate (DOP), and isododecyl pelargonate (IDP).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020170048444A KR101855040B1 (en) | 2017-04-14 | 2017-04-14 | Method for manufacturing of pressable polymer-bonded explosives using water-based polymer emulsion and pressable polymer-bonded explosives by the same |
PCT/KR2018/004340 WO2018190673A1 (en) | 2017-04-14 | 2018-04-13 | Method for manufacturing compressed composite gunpowder using polymer emulsion, and compressed composite gunpowder manufactured thereby |
Publications (3)
Publication Number | Publication Date |
---|---|
EP3611152A1 EP3611152A1 (en) | 2020-02-19 |
EP3611152A4 EP3611152A4 (en) | 2020-04-29 |
EP3611152B1 true EP3611152B1 (en) | 2024-02-07 |
Family
ID=62199183
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP18784066.5A Active EP3611152B1 (en) | 2017-04-14 | 2018-04-13 | Method for manufacturing compressed composite gunpowder using polymer emulsion, and compressed composite gunpowder manufactured thereby |
Country Status (4)
Country | Link |
---|---|
US (1) | US20180297909A1 (en) |
EP (1) | EP3611152B1 (en) |
KR (1) | KR101855040B1 (en) |
WO (1) | WO2018190673A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115073246B (en) * | 2022-07-05 | 2023-09-01 | 神木北方特能化工科技有限公司 | Blow-drying device and method for emulsion explosive production line |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2031677A5 (en) * | 1969-02-04 | 1970-11-20 | France Etat | Explosive mixtures contg metals prepn |
DE3614173C1 (en) * | 1986-04-26 | 1989-03-02 | Dynamit Nobel Ag | Granulated, stabilized alpha and beta octogen and process for the production of alpha octogen |
US5358587A (en) * | 1991-07-01 | 1994-10-25 | Voigt Jr H William | Simplified emulsion coating of crystalline explosives in a TNT melt |
KR100255359B1 (en) * | 1997-12-27 | 2000-05-01 | 최동환 | Pressable plastic bonded explosive formulation using hytemp/doa as a binder its preparing method |
NO318866B1 (en) * | 2003-10-06 | 2005-05-18 | Dyno Nobel Asa | Compressible plastic bonded explosive composition |
US20050183803A1 (en) * | 2004-01-13 | 2005-08-25 | Akester Jeffrey D. | Explosive molding powder slurry processing in a nonaqueous medium using a mixed solvent lacquer system |
NO321356B1 (en) * | 2004-05-06 | 2006-05-02 | Dyno Nobel Asa | Compressible explosive composition |
KR101225915B1 (en) * | 2009-05-12 | 2013-01-24 | 주식회사 엘지화학 | Method for preparing of acrylonitrile-butadiene latex |
KR101182328B1 (en) * | 2010-08-18 | 2012-09-20 | 국방과학연구소 | High density and high performance plastic bonded explosive and the fabrication method thereof |
KR101444658B1 (en) * | 2014-04-15 | 2014-10-28 | 국방과학연구소 | Nitrogen-rich 4,4'-(ethane-1,2-yl)bis(5-nitroiminotetrazol-1-ate) organic salts based plastic bonded explosive formulations |
-
2017
- 2017-04-14 KR KR1020170048444A patent/KR101855040B1/en active IP Right Grant
-
2018
- 2018-04-12 US US15/951,476 patent/US20180297909A1/en not_active Abandoned
- 2018-04-13 EP EP18784066.5A patent/EP3611152B1/en active Active
- 2018-04-13 WO PCT/KR2018/004340 patent/WO2018190673A1/en active Application Filing
Also Published As
Publication number | Publication date |
---|---|
EP3611152A4 (en) | 2020-04-29 |
US20180297909A1 (en) | 2018-10-18 |
WO2018190673A1 (en) | 2018-10-18 |
EP3611152A1 (en) | 2020-02-19 |
KR101855040B1 (en) | 2018-05-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9919305B2 (en) | Sulfonyl-containing polymeric material with rigid and contorted divinyl crosslinker | |
EP3611152B1 (en) | Method for manufacturing compressed composite gunpowder using polymer emulsion, and compressed composite gunpowder manufactured thereby | |
CN103980073B (en) | A kind of preparation method of containing hydrogenated cerium high heat explosive | |
WO2014124774A1 (en) | Bead polymer for producing pmi foams | |
CN112028719B (en) | Method for recovering waste particles of molding powder | |
US3956038A (en) | Process for obtaining coated pyrotechnic compositions | |
NO321356B1 (en) | Compressible explosive composition | |
WO2018133174A1 (en) | Preparation method for high-purity dibutyltin oxide | |
US9463454B2 (en) | Amino-containing polymeric material with rigid and contorted divinyl crosslinker | |
RU2451652C2 (en) | Method of producing spherical powder for 5,6 mm-sporting caliber cartridges with annular ignition | |
CN110937963B (en) | Low-detonation-velocity mixed explosive and preparation method thereof | |
US2771035A (en) | Propellant | |
KR101182328B1 (en) | High density and high performance plastic bonded explosive and the fabrication method thereof | |
EP3637037B1 (en) | Method for synthesizing nanodiamond using an explosive body | |
CN114395074B (en) | Organic-inorganic hybrid fluid loss agent for oil well cement, preparation method and application | |
KR20160125746A (en) | Preparation method for submicron and micron size- spherical rdx particles, and spherical rdx particles prepared by the same | |
CN110845285A (en) | Method for reducing hygroscopicity of ammonium perchlorate | |
CN108976095B (en) | C L-20 base pressure-loaded high-energy insensitive explosive and preparation method thereof | |
US2371879A (en) | Explosive charge | |
CN108218642B (en) | Heat-resistant anti-caking superfine ammonium nitrate and preparation method thereof | |
US7857922B2 (en) | Pressable plastic-bound explosive composition | |
CN108687354B (en) | Preparation method of high-activity Ti/2B nano powder | |
US2888713A (en) | Method of preparing globular propellant powder | |
KR101823820B1 (en) | Priming composition for initiators, and initiators priming using the same | |
NO321217B1 (en) | Process for manufacturing explosive charges |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20190919 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
A4 | Supplementary search report drawn up and despatched |
Effective date: 20200327 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C06B 23/00 20060101ALI20200324BHEP Ipc: C06B 25/20 20060101ALI20200324BHEP Ipc: C06B 21/00 20060101ALI20200324BHEP Ipc: C06B 45/22 20060101AFI20200324BHEP Ipc: C06B 33/00 20060101ALI20200324BHEP Ipc: C06B 47/14 20060101ALI20200324BHEP |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20210715 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20230830 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602018064957 Country of ref document: DE |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20240319 Year of fee payment: 7 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20240319 Year of fee payment: 7 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20240207 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240607 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240207 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240429 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240508 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1655284 Country of ref document: AT Kind code of ref document: T Effective date: 20240207 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240507 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240207 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240207 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240207 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240207 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CZ Payment date: 20240405 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240507 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240507 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240207 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240207 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240607 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240207 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240508 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240207 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240207 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240207 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240207 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240207 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240607 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240207 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240607 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240207 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240207 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240207 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20240207 |