EP3515881A1 - Composite pyrotechnic product containing an anti-gleam agent of potassium salt type - Google Patents
Composite pyrotechnic product containing an anti-gleam agent of potassium salt typeInfo
- Publication number
- EP3515881A1 EP3515881A1 EP17787216.5A EP17787216A EP3515881A1 EP 3515881 A1 EP3515881 A1 EP 3515881A1 EP 17787216 A EP17787216 A EP 17787216A EP 3515881 A1 EP3515881 A1 EP 3515881A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- potassium
- agent
- composite pyrotechnic
- pyrotechnic product
- energetic
- 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.)
- Granted
Links
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 61
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011591 potassium Substances 0.000 claims abstract description 30
- 239000011230 binding agent Substances 0.000 claims abstract description 29
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 27
- 239000004014 plasticizer Substances 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 229910001610 cryolite Inorganic materials 0.000 claims abstract description 16
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 claims abstract description 11
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 9
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 9
- 239000001472 potassium tartrate Substances 0.000 claims abstract description 8
- 229940111695 potassium tartrate Drugs 0.000 claims abstract description 8
- 235000011005 potassium tartrates Nutrition 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 239000000945 filler Substances 0.000 claims abstract description 5
- 239000003380 propellant Substances 0.000 claims description 52
- 238000002485 combustion reaction Methods 0.000 claims description 34
- 239000000654 additive Substances 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 20
- 238000004132 cross linking Methods 0.000 claims description 15
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 15
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 9
- 239000000028 HMX Substances 0.000 claims description 7
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 claims description 7
- 239000004449 solid propellant Substances 0.000 claims description 6
- POCJOGNVFHPZNS-ZJUUUORDSA-N (6S,7R)-2-azaspiro[5.5]undecan-7-ol Chemical compound O[C@@H]1CCCC[C@]11CNCCC1 POCJOGNVFHPZNS-ZJUUUORDSA-N 0.000 claims description 5
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 claims description 5
- BSPUVYFGURDFHE-UHFFFAOYSA-N Nitramine Natural products CC1C(O)CCC2CCCNC12 BSPUVYFGURDFHE-UHFFFAOYSA-N 0.000 claims description 5
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000010348 incorporation Methods 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229940095064 tartrate Drugs 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012258 stirred mixture Substances 0.000 claims 2
- 229920006037 cross link polymer Polymers 0.000 abstract description 2
- 150000001540 azides Chemical class 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 12
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 11
- 229910052939 potassium sulfate Inorganic materials 0.000 description 11
- 230000001133 acceleration Effects 0.000 description 9
- 239000003517 fume Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000010304 firing Methods 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- RUKISNQKOIKZGT-UHFFFAOYSA-N 2-nitrodiphenylamine Chemical compound [O-][N+](=O)C1=CC=CC=C1NC1=CC=CC=C1 RUKISNQKOIKZGT-UHFFFAOYSA-N 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Inorganic materials [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 5
- IPPYBNCEPZCLNI-UHFFFAOYSA-N trimethylolethane trinitrate Chemical compound [O-][N+](=O)OCC(C)(CO[N+]([O-])=O)CO[N+]([O-])=O IPPYBNCEPZCLNI-UHFFFAOYSA-N 0.000 description 5
- QUAMCNNWODGSJA-UHFFFAOYSA-N 1,1-dinitrooxybutyl nitrate Chemical compound CCCC(O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QUAMCNNWODGSJA-UHFFFAOYSA-N 0.000 description 4
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 4
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 239000001120 potassium sulphate Substances 0.000 description 3
- 235000011151 potassium sulphates Nutrition 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- LYAGTVMJGHTIDH-UHFFFAOYSA-N diethylene glycol dinitrate Chemical compound [O-][N+](=O)OCCOCCO[N+]([O-])=O LYAGTVMJGHTIDH-UHFFFAOYSA-N 0.000 description 2
- FUHQFAMVYDIUKL-UHFFFAOYSA-N fox-7 Chemical group NC(N)=C([N+]([O-])=O)[N+]([O-])=O FUHQFAMVYDIUKL-UHFFFAOYSA-N 0.000 description 2
- 229960003711 glyceryl trinitrate Drugs 0.000 description 2
- 159000000011 group IA salts Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QCOXCILKVHKOGO-UHFFFAOYSA-N n-(2-nitramidoethyl)nitramide Chemical compound [O-][N+](=O)NCCN[N+]([O-])=O QCOXCILKVHKOGO-UHFFFAOYSA-N 0.000 description 2
- XIFJZJPMHNUGRA-UHFFFAOYSA-N n-methyl-4-nitroaniline Chemical compound CNC1=CC=C([N+]([O-])=O)C=C1 XIFJZJPMHNUGRA-UHFFFAOYSA-N 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- KYKNRZGSIGMXFH-YGEZSCCGSA-M potassium;(2s,3s)-2,3,4-trihydroxy-4-oxobutanoate Chemical compound [K+].OC(=O)[C@@H](O)[C@H](O)C([O-])=O KYKNRZGSIGMXFH-YGEZSCCGSA-M 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- AGCQZYRSTIRJFM-UHFFFAOYSA-N triethylene glycol dinitrate Chemical compound [O-][N+](=O)OCCOCCOCCO[N+]([O-])=O AGCQZYRSTIRJFM-UHFFFAOYSA-N 0.000 description 2
- -1 2,2-dinitropropyl Chemical group 0.000 description 1
- FXYYVODGZXUHLT-UHFFFAOYSA-N 2h-tetrazol-5-ylhydrazine Chemical compound NNC=1N=NNN=1 FXYYVODGZXUHLT-UHFFFAOYSA-N 0.000 description 1
- MZRUFMBFIKGOAL-UHFFFAOYSA-N 5-nitro-1h-pyrazole Chemical compound [O-][N+](=O)C1=CC=NN1 MZRUFMBFIKGOAL-UHFFFAOYSA-N 0.000 description 1
- 241000928106 Alain Species 0.000 description 1
- 230000005457 Black-body radiation Effects 0.000 description 1
- NDYLCHGXSQOGMS-UHFFFAOYSA-N CL-20 Chemical compound [O-][N+](=O)N1C2N([N+]([O-])=O)C3N([N+](=O)[O-])C2N([N+]([O-])=O)C2N([N+]([O-])=O)C3N([N+]([O-])=O)C21 NDYLCHGXSQOGMS-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- SQSPRWMERUQXNE-UHFFFAOYSA-N Guanylurea Chemical compound NC(=N)NC(N)=O SQSPRWMERUQXNE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 1
- 239000000006 Nitroglycerin Substances 0.000 description 1
- VAALVBPLSFRYMJ-XXMNONFOSA-N O=C1OC(=O)[C@@H]([C@@H](C23)C4)[C@H]1[C@@H]4C3[C@@H]1C[C@H]2[C@H]2C(=O)OC(=O)[C@@H]12 Chemical compound O=C1OC(=O)[C@@H]([C@@H](C23)C4)[C@H]1[C@@H]4C3[C@@H]1C[C@H]2[C@H]2C(=O)OC(=O)[C@@H]12 VAALVBPLSFRYMJ-XXMNONFOSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- JBXIZHBJVGYZCD-UHFFFAOYSA-N [N+](=O)(O)[O-].[N+](=O)(O)[O-].[N+](=O)(O)[O-].C(CCC)(O)O Chemical compound [N+](=O)(O)[O-].[N+](=O)(O)[O-].[N+](=O)(O)[O-].C(CCC)(O)O JBXIZHBJVGYZCD-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- KUNXCAIGAVGORW-UHFFFAOYSA-N n-ethyl-n-[[ethyl(nitro)amino]methyl]nitramide Chemical compound CCN([N+]([O-])=O)CN(CC)[N+]([O-])=O KUNXCAIGAVGORW-UHFFFAOYSA-N 0.000 description 1
- NQPFICHAHMRTNV-UHFFFAOYSA-N n-ethyl-n-[[methyl(nitro)amino]methyl]nitramide Chemical compound CCN([N+]([O-])=O)CN(C)[N+]([O-])=O NQPFICHAHMRTNV-UHFFFAOYSA-N 0.000 description 1
- QKVCTKJCIMPZEI-UHFFFAOYSA-N n-methyl-n-[[methyl(nitro)amino]methyl]nitramide Chemical compound [O-][N+](=O)N(C)CN(C)[N+]([O-])=O QKVCTKJCIMPZEI-UHFFFAOYSA-N 0.000 description 1
- MJVUDZGNBKFOBF-UHFFFAOYSA-N n-nitronitramide Chemical compound [O-][N+](=O)N[N+]([O-])=O MJVUDZGNBKFOBF-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- KYKNRZGSIGMXFH-ZVGUSBNCSA-M potassium bitartrate Chemical compound [K+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O KYKNRZGSIGMXFH-ZVGUSBNCSA-M 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/04—Compositions characterised by non-explosive or non-thermic constituents for cooling the explosion gases including antifouling and flash suppressing agents
-
- 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
- C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
- C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
- C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
- C06B45/105—The resin being a polymer bearing energetic groups or containing a soluble organic explosive
Definitions
- the present invention relates to composite pyrotechnic products, particularly suitable as solid propellants for propelling tactical missiles. It is more precisely composite pyrotechnic products, containing a high rate of organic energy charges in an energy binder.
- the composition of said products is optimized with reference to the technical problem of the discretion of said products during their combustion, more specifically with reference to the technical problem of obtaining an interesting compromise in terms of discretion and energy power.
- a so-called acceleration phase where the operating pressure is maximum (the value of this maximum operating pressure being obviously related to the energy power of the propellant in combustion) and a so-called cruise phase where the operating pressure is minimal (generally of the order of 2 to 3 MPa);
- cryolite Na 3 AIF 6
- potassium and aluminum fluoride potassium cryolite, (K 3 AIF 6 )
- K 3 AIF 6 potassium cryolite,
- potassium cryolite K 3 AIF 6
- alkaline salts such as potassium sulphate (K 2 SO 4 ), potassium nitrate, potassium fluoride and aluminum fluoride
- potassium cryolite (K 3 AIF 6 ) potassium cryolite (K 3 AIF 6 )
- hydrogenated potassium tartrate as anti-glare additives
- sodium cryolite K 3 AIF 6
- tartrate of hydrogenated potassium as anti-glare additives
- K 3 AIF 6 potassium cryolite
- compositions typically contain essentially energetic fillers, nitrocellulose, cellulose acetate butyrate, an energetic plasticizer, and additives. They may also contain at least one additional energetic binder such as glycidyl polyazide (PAG; non-crosslinked) or non-energetic such as polybutadiene with terminal hydroxyl functions (PBHT).
- PAG glycidyl polyazide
- PBHT polybutadiene with terminal hydroxyl functions
- the double-base solid propellants have a more modest energy performance than the composite propellants developed in a second time.
- composite propellants such as Nitramite ® and Azamite ® .
- Composite propellants of Nitramite ® type contain energetic charges (of the RDX or HMX type) in a crosslinked binder (of polyester, polyether or polycaprolactone type), plasticized with nitroglycerine.
- their composition has been optimized in that it does not contain metal charges (such as aluminum charges) able to generate primary fumes, no or little inorganic energy charges (such as ammonium perchlorate charges) capable of generating secondary fumes and in that it contains effective anti-their agents capable of minimizing or even eliminate the phenomena of post combustion (it is noted here incidentally that the nature and quantity of anti-light agents are to be optimized insofar as said anti-glare agents are capable of generating primary and / or secondary fumes).
- Composite propellants of the Azamite ® type are even more energetic propellants than those of the Nitramite ® type. They contain energetic charges (of the RDX or HMX type) in a crosslinked energy binder (of the glycidyl polyazide type (PAG)), plasticized with at least one energetic plasticizer. They are opportunely used up to firing pressures of the order of 16 MPa, in so-called acceleration phase. Under such conditions, the anti-light agents of the prior art (see above) have proved to be ineffective (in particular to substantially reduce the post-combustion phenomenon, more generally with reference to the technical problem of discretion).
- the present invention thus relates to new composite pyrotechnic products, highly energetic. They are of the crosslinked energy binder type containing organic energy charges. They contain, more specifically, in a plasticized binder comprising a crosslinked energy polymer and at least one energetic plasticizer, organic energetic fillers and at least one anti-glow agent of the potassium salt type. Characteristically:
- said crosslinked energy polymer consists of a glycidyl polyazide (PAG) having a number-average molecular weight
- said at least one anti-glow agent of the potassium salt type is chosen from potassium cryolite (K3AIF 6 ), potassium monobasic tartrate (C4H5KO6) and mixtures thereof.
- the structure of the composite pyrotechnic products of the invention therefore typically associates a specific binder (energetic) and at least one specific anti-glare agent (potassium salt type).
- the nature of the binder (that of its precursor (energetic) polymer) therefore constitutes one of the key elements (of the composition) of the composite pyrotechnic products of the invention.
- potassium cryolite K 3 AIF 6
- monobasic potassium tartrate C 4 H 5 KO 6
- said monobasic potassium tartrate advantageously consisting of monobasic potassium L-tartrate (see above)
- potassium cryolite K 3 AIF 6
- the infra-red signature of said potassium cryolite is more discrete than that of said monobasic potassium tartrate.
- Said at least one original anti-glare agent is obviously conveniently present in an effective amount but not excessive (the (s) added potassium salt (s) suitable for minimizing the phenomenon of post combustion but likely to generate primary fumes and, in any case, have a negative influence on the energy output).
- This effective and non-excessive amount is generally such that it provides in the composition of the product a potassium content of 0.2 to 5% by weight, preferably 0.2 to 2.5% by weight.
- This advantageous potassium content of 0.2 to 2.5% by weight corresponds approximately to a mass content, in one and / or the other of said specific potassium salts, of 1 to 5%. It is conceivable that at the desired potassium equivalent content, the required dHsKOe content is higher than that required in K3AIF6.
- binder energy binder, therefore
- precursor polymer hydroxytelechelic glycidyl polyazide
- the "one" glycidyl polyazide should read “at least one" glycidyl polyazide throughout the present text. Indeed, it is in no way excluded from the scope of the invention to use a mixture of at least two glycidyl polyazides (having molecular weights (between 700 and 3000 g / mol) and / or different branching ratios). as precursor polymer of the binder of the products of the invention.
- the precursor energy polymer of the binder of the products of the invention is therefore a polyazide, a glycidyl polyazide (PAG) which has terminal hydroxy functions (a hydroxytelechelic PAG); hence 1) its energetic properties and 2) its ability to be crosslinked with the polyisocyanate crosslinking agents.
- PAG glycidyl polyazide
- Said polymer has an adequate molecular weight (in particular, with reference to its consistency (liquid) and the consistency of its mixture with essentially the (organic energy) charges and in particular reference to the relative content of the crosslinked binder in crosslinking agent (s)), a number-average molecular weight (Mn) of between 700 and 3000 g / mol, advantageously between 1700 and 2300 g / mol.
- Mn number-average molecular weight
- Crosslinking agents of the polyisocyanate type (at least bifunctional), which are suitable for the crosslinking of such a hydroxytelechelic glycidyl polyazide (PAG), are known per se. It may especially be di- or triisocyanates.
- liquid polyisocyanates chosen from toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), dicyclohexyl methylene diisocyanate (MDCl), hexamethylene diisocyanate (HDI), trimer of said hexamethylene diisocyanate (especially marketed by Bayer under the trade name Desmodur ® N 3300), biuret trihexane isocyanate (BTHI), the S ⁇ - ⁇ -hexamethylene trimethyl-diisocyanate and mixtures thereof.
- the trimer of hexamethylene diisocyanate is used.
- Said crosslinking agents are conventionally used in an amount necessary and sufficient to ensure the crosslinking of the polymer (not excessive so as not to pollute the crosslinked product obtained). They are conventionally used in an amount such that the bridging ratio (NCO (of the crosslinking agent) / OH (of the polymer)) is between 0.8 and 1.4, or advantageously 1.2.
- the crosslinked energy polymer generally represents from 9 to 14% by weight of the total composition of the composite pyrotechnic products of the invention.
- the energy polymer per is generally involved for 7 to 12% by weight, the at least one crosslinking agent for about 2% by weight.
- binder of its precursor polymer
- the interest of the invention is based on the combination of such an energetic binder precursor polymer with at least one specific anti-glare agent (potassium salt type).
- the energy binder is associated with at least one energetic plasticizer.
- the energy plasticizer (s) in question is (are) advantageously of the nitrate and / or nitramine type.
- the energy plasticizer (s) in question is (are) very advantageously selected from diethylene glycol dinitrate (DEGDN), triethylene glycol dinitrate (TEGDN), butanetriol trinitrate (BTTN) trimethylolethane trinitrate (TMETN), a mixture of 2,4-dinitro-2,4-diaza-pentane, 2,4-dinitro-2,4-diaza-hexane and 3,5-dinitro-3, 5-diaza-heptane (and especially DNDA 5.7), nitrato ethyl nitramines (especially methyl-2-nitratoethyl nitramine (methylNENA) and ethyl-2-nitratoethyl nitramine (ethylNENA)
- the plasticizer (s) of the pyrotechnic products of the invention generally represent (s) from 10 to 30% by weight, more generally from 15 to 25% by weight, of the total composition of said products.
- the energy charges present are organic charges.
- the organic energy charges involved are not per se original. These are known organic energy charges Persian and, for the most part, already packaged according to the prior art in crosslinked energy polymer binders (in particular PAG type). It is advantageously charges of hexogen (RDX), octogen (HMX), hexanitrohexaazaisowurtzitane (CL20), nitroguanidine (NGU), ethylene dinitramine (EDNA), dinitramide N-guanylurea (FOX 12 (GUDN)), 1,1-diamino-2,2-dinitroethylene (FOX 7 (DADE)), 5,5'-azotetrazolate bis (triaminoguanidinium) (TAGZT), 5,5'- Dihydrazinium azotetrazolate (DHDZT), 5,5'-bis (tetrazolyl) hydrazine (HBT), bis (2,2-dinitropropyl) nitramine (BDNPN), a nitropyrazole or
- energy charges of RDX and / or H MX there are energy charges of RDX and / or H MX, more preferably energy charges of RDX or HMX.
- hexogen charges and / or octogen charges are particularly recommended since these two types of charges offer a very satisfactory compromise: safety / energy efficiency and where it is also possible to take advantage of the scope of the invention, assets (resulting from the use of these two types of charges in the prior art).
- Organic energy charges are conventionally in the form of solid grains, distributed homogeneously within the plasticized crosslinked binder. These solid grains suitably have, in a known manner per se, several particle size distributions.
- the organic energy charges of the pyrotechnic products of the invention generally represent from 50 to 70% by weight, more generally from 55 to 65% by weight, of the total composition of said products. It is understood that said products are high load.
- metal charges aluminum in particular
- Such metal charges are indeed likely to generate particles during their combustion, ie to generate primary fumes.
- inorganic energy charges of ammonium perchlorate, in particular
- inorganic energy charges are necessarily, in reference to the discretion sought, in small quantities ( ⁇ 4% by weight). They can be considered as additives (see below). Their presence may be appropriate, with reference to the ballistic properties of the product.
- the composite pyrotechnic products of the invention are moreover likely to contain, and generally contain, in their binder (crosslinked precursor polymer), in addition to plasticizers, organic energy charges and specific anti-glare agent (s). ), at least one additive. It is more apt to speak of at least one other additive, the anti-glare agents being quite capable of being analyzed as additives.
- the anti-glare agents have been presently isolated from the other additives, insofar as they are present with reference to the technical problem currently considered and where they therefore constitute a key element of the products of the invention.
- the composite pyrotechnic products of the invention therefore contain in their composition, in addition to the crosslinked polymer (PAG), the plasticizers (s), organic energy charges and the at least one specific anti-glare agent, at least one additive; said at least one additive comprising at least one crosslinking catalyst and / or at least one stabilizing agent of the plasticizer (s) present (s) and / or at least one combustion catalyst.
- Said at least one polymerization catalyst may especially be chosen from triphenylbismuth and tin dibutyldilaurate (DBTL). Present, it is generally at a content not exceeding 100 ppm.
- Said at least one stabilizing agent for the plasticizer (s) present) may especially consist of at least one aromatic amine, such as 2-nitrodiphenylamine (2-NDPA) and N-methylparanitroaniline (MNA). Present, it is generally at a content of about 1% by weight.
- Said at least one combustion catalyst may especially be chosen from conventional combustion catalysts, such as lead salts and oxides, and bismuth citrate. Said bismuth citrate, especially because of its lower toxicity, is preferred.
- the Applicant has described, in the patent application WO 2016/066245, the advantageous use of said citrate of bismuth as a combustion catalyst.
- Said at least one combustion catalyst is generally present in the composition of the pyrotechnic products of the invention at a mass ratio of 1 to 6%, very generally at a mass ratio of 3 to 5%.
- additives that may be present in the composition of the composite pyrotechnic products of the invention may especially consist of inorganic energetic charges (see above) and one or more implementing agents (auxiliaries). manufacturing).
- the said agent (s) is (are) generally present at a content of 1 to 2% by weight.
- the additives which may be present (in view of the above remarks, it has been understood that generally several types of additive are present) generally represent a maximum of 10% by weight of the composition of the composite pyrotechnic products of the invention. They generally represent from 0.1 to 10% by weight (often from 1.5 to 10% by weight) of the composition of said composite pyrotechnic products of the invention.
- the composite pyrotechnic products of the invention are not of a new type but that they are new by the combination, in their composition, of a specific binder (PAG crosslinked with at least one polyisocyanate) and at least one specific anti-glare agent.
- a specific binder PAG crosslinked with at least one polyisocyanate
- at least one specific anti-glare agent PAG crosslinked with at least one polyisocyanate
- composition of the composite pyrotechnic products of the invention thus contains:
- said at least one antiglare potassium salt type selected from the potassium cryolite agent (K 3 AIF 6) monobasic potassium tartrate (QHSKO O) and mixtures thereof, in an amount ensuring a potassium content of said propellant from 0.2% to 2.5% by weight.
- K 3 AIF 6 potassium cryolite agent
- QHSKO O monobasic potassium tartrate
- the advantageous ranges indicated above can quite be considered independently of each other. Preferably, they are in combination with each other.
- said composition is generally free of any other ingredient (especially any metallic filler) and therefore consists of the ingredients listed above, present in the amounts indicated above.
- composite pyrotechnic products are particularly suitable as solid propellants for propellant loading of tactical missiles. Their use for this purpose is particularly recommended. It is an integral part of the present invention.
- the present invention therefore also relates to a method for preparing a composite pyrotechnic product as described above.
- This process comprises:
- the at least one anti-glare agent is introduced in powder form.
- the partial vacuum mentioned is intended for degassing of the medium above which it is applied. It is usually 10 mm Hg. Incidentally, it is not necessarily constant intensity.
- the heat treatment (crosslinking (of the hydroxytelechelic PAG)) is generally carried out at a temperature between 30 and 60 ° C (30 ° C ⁇ T ⁇ 60 ° C) for several days.
- FIGS. 1, 2 and 3 show, for each of the propellants tested (respectively that of Comparative Example C2 (with K 2 SO 4 (15 pm)), that of Example 1 and that of Example 2). the temperature (equivalent black body radiation temperature (° C)) according to the axis of the jet (of generated gases) as a function of the distance (measured distance (in m) from the outlet of the nozzle); the propellant tested being at an operating pressure of 16 MPa (see point 5 below).
- the longitudinal thermal profiles shown were obtained using IR cameras on Band II. These cameras made it possible to draw a two-dimensional thermal profile of the jet emitted by the nozzle.
- Examples 1 and 2 relate to propellants according to the invention comprising, in their composition:
- RDX - hexogen charges
- the oxidizing charge of hexogen is conventional: it consists of 60% by weight of a RDX of a particle size class of 0 - 100 ⁇ m and 40% by weight of a RDX of a particle size class of 2.5 ⁇ m. 5 pm;
- BTTN trinitrate butanediol
- TMETN trimethylolethane trinitrate
- NINA N-methylparanitroaniline
- 2-NDPA 2-nitrodiphenylamine
- an anti-glare agent K 2 AIF 6 for example 1 of the invention and C4H5KO6 for example 2 of the invention.
- the anti-glare agents were present in the propellant compositions (Comparative Examples C1 and C2 and Examples 1 and 2 of the invention), with almost iso-content (approximately 0.9% by weight) of potassium.
- compositions of each of said propellants are shown in Table 1 below. We can more precisely speak about compositions mass of the precursor paste of each of said propellants (before crosslinking).
- the crosslinking catalyst (DBTL (dibutyltin dilaurate) (55 ppm) was then added to said homogeneous paste and the medium was further stirred 30 min before the addition of the binder crosslinking agent (Desmodur ® N 3300). Said crosslinking agent was finally added and the medium was stirred for 15 minutes (still at 50 ° C. and under vacuum).
- DBTL dibutyltin dilaurate
- the batches of 800 g of pulp were partly used to assess the feasibility of the process of obtaining the propellants (to measure the pot life of the dough) and partly, after crosslinking, to evaluate the ballistic behavior of the propellant (for measure the burning rate of it).
- the batches of 5 kg, divided in two, were crosslinked.
- two blocks of propellants were prepared: two blocks of diameter 90 mm and length 150 mm. They have been tested (on the test bench: see point 5 below).
- the pot life (which makes it possible to assess the feasibility of the process for obtaining the propellants) was determined by measuring the viscosity of the propellant paste in question (containing the crosslinking agent and the crosslinking catalyst) at over time, using a Brookfield viscometer (with the body No. 3 (mobile C) rotated at 1 rpm), at a temperature of 50 ° C. The time for which the viscosity reached 15 kPo was recorded to determine if the propellant met the industrialization criterion, i.e. if the said time was greater than 10 h. 4. DETERMINATION OF COMBUSTION SPEED OF PROPERGOLS
- the burning rate was measured conventionally at 20 ° C and 10 MPa.
- Some characteristics of the jet have been determined by optronic means, in particular by IR Band II observation, visible transmission / emission (at 632 nm), and transmission / emission in IR between 2 and 14 ⁇ m.
- the longitudinal thermal profiles obtained by IR camera (Band II) make it possible to highlight in the jet gradients in black body equivalent temperature.
- the levels of transmission in the visible and in the IR make it possible to highlight the notion of transparency and thus the effectiveness of the anti-light agents tested.
- Example 1 of the invention For the propellant according to Example 1 of the invention, the composition of which contained K 3 AIF 6 , no post-combustion flame was detected. The jet was considered inert. The level of radiation in band II remained low: the maximum blackbody equivalent temperature was 600 ° C at the nozzle outlet (it did not exceed this value by moving away from the outlet plane of said nozzle).
- Example 2 of the invention For the propellant according to Example 2 of the invention, the composition of which contained C4H5KO6, in the same way, no post-combustion flame was detected.
- the jet was considered inert.
- the level of radiation in band II remained low: the temperature
- the maximum equivalent blackbody was 650 ° C at the nozzle outlet (it did not exceed this value by moving away from the exit plane of said nozzle). This maximum temperature is a little higher than that obtained with K 3 AIF 6 .
Abstract
The main subject of the present invention is a composite pyrotechnic product containing, in a plasticized binder comprising an energetic crosslinked polymer and at least one energetic plasticizer, organic energetic fillers and at least one anti-gleam agent of potassium salt type. Characteristically, said crosslinked energetic polymer consists of a polyglycidyl azide (PGA), having a number-average molecular weight (Mn) of between 700 and 3000 g/mol, crosslinked, via its hydroxyl end functions, to at least one crosslinking agent of polyisocyanate type, and said at least one anti-gleam agent of potassium salt type is selected from potassium cryolite (K3AIF6), monobasic potassium tartrate (C4H5KO6), and mixtures thereof. The composite pyrotechnic product in question is beneficial in terms of discretion and energetic power.
Description
Produit pyrotechnique composite renfermant un agent anti-lueur de type sel de potassium Composite pyrotechnic product containing a potassium salt-type anti-glare agent
La présente invention concerne des produits pyrotechniques composites, convenant notamment comme propergols solides pour chargements propulsifs de missiles tactiques. Il s'agit plus précisément de produits pyrotechniques composites, renfermant un fort taux de charges énergétiques organiques dans un liant énergétique. La composition desdits produits est optimisée en référence au problème technique de la discrétion desdits produits lors de leur combustion, plus précisément en référence au problème technique de l'obtention d'un compromis intéressant en termes de discrétion et de pouvoir énergétique. The present invention relates to composite pyrotechnic products, particularly suitable as solid propellants for propelling tactical missiles. It is more precisely composite pyrotechnic products, containing a high rate of organic energy charges in an energy binder. The composition of said products is optimized with reference to the technical problem of the discretion of said products during their combustion, more specifically with reference to the technical problem of obtaining an interesting compromise in terms of discretion and energy power.
Le problème technique de la discrétion (des propergols solides des chargements propulsifs) des missiles est un réel problème technique. The technical problem of stealth (propellant propellant propellants) missiles is a real technical problem.
Il est bien connu de l'homme du métier : It is well known to those skilled in the art:
- qu'ils existent deux phases de tir, lors du tir d'un missile tactique : une phase dite d'accélération où la pression de fonctionnement est maximale (la valeur de cette pression de fonctionnement maximale étant évidemment liée au pouvoir énergétique du propergol en combustion) et une phase dite de croisière où la pression de fonctionnement est minimale (généralement de l'ordre de 2 à 3 MPa) ; - that there exist two firing phases, when firing a tactical missile: a so-called acceleration phase where the operating pressure is maximum (the value of this maximum operating pressure being obviously related to the energy power of the propellant in combustion) and a so-called cruise phase where the operating pressure is minimal (generally of the order of 2 to 3 MPa);
- que la discrétion d'un missile tactique, i.e. celle de son chargement de propergol s'apprécie à l'aptitude dudit chargement, lors de sa combustion, à émettre des fumées (fumées primaires (résultant de la combustion, dans le jet de gaz produit, des particules solides également produites) et/ou fumées secondaires (si du perchlorate d'ammonium est présent dans la composition du propergol)) et à engendrer des lueurs
(dues au phénomène de post combustion, i.e. à la ré-inflammation des gaz de combustion) ; et - that the discretion of a tactical missile, ie that of its propellant charge is assessed to the ability of said loading, during its combustion, to emit fumes (primary fumes (resulting from combustion, in the jet of gas) product, solid particles also produced) and / or secondary fumes (if ammonium perchlorate is present in the propellant composition)) and to generate glow (due to the phenomenon of post combustion, ie to the re-ignition of the combustion gases); and
- que ladite discrétion est évidemment plus difficile à gérer en phase dite d'accélération. - that said discretion is obviously more difficult to manage in so-called acceleration phase.
Dans ce contexte de la combustion des propergols, en référence au problème technique de la discrétion, voire à un problème technique de nature différente, il a été préconisé d'incorporer divers types d'additifs dans la composition de propergols. In this context of the combustion of propellants, with reference to the technical problem of discretion, or even to a technical problem of a different nature, it has been recommended to incorporate various types of additives in the composition of propellants.
Dans un premier temps, pour notamment les missiles tactiques, des propergols double base (nitrocellulose/nitroglycérine) ont été développés. De tels propergols, économiques à produire et très discrets (grâce à la présence, au sein de leur composition, d'additifs (agents anti-lueurs) performants), sont toujours d'actualité. Initially, for tactical missiles in particular, double base propellants (nitrocellulose / nitroglycerin) have been developed. Such propellants, economical to produce and very discreet (thanks to the presence in their composition of additives (anti-glare agents) performance), are still relevant.
Dans ce contexte des propergols solides double base, il a notamment été décrit : In this context, double base solid propellants have been described in particular:
- l'utilisation de cryolite (Na3AIF6) et de fluorure de potassium et d'aluminium (= de cryolithe de potassium ; (K3AIF6)), comme additifs réduisant le flash émis au moment d'un tir d'arme à feu (voir la partie introductive du brevet US 4 078 955). De tels additifs, efficaces, présentent toutefois l'inconvénient (dans ce contexte) de générer, lors de la combustion, de l'alumine et des fluorures, qui provoquent usure et corrosion dans le canon ; - the use of cryolite (Na 3 AIF 6 ) and potassium and aluminum fluoride (= potassium cryolite, (K 3 AIF 6 )), as additives reducing the flash emitted at the time of a shot of firearm (see introductory part of US Pat. No. 4,078,955). However, such effective additives have the drawback (in this context) of generating, during combustion, alumina and fluorides, which cause wear and corrosion in the barrel;
- l'utilisation de cryolite de potassium (K3AIF6), comme catalyseur de combustion et celle de sels alcalins, tels le sulfate de potassium (K2S04), le nitrate de potassium, le fluorure de potassium et d'aluminium (= la cryolithe de potassium ; (K3AIF6)), le tartrate de potassium hydrogéné, comme additifs anti-lueurs (voir l'enseignement du brevet US 4 381 270) ;
- l'utilisation de ces mêmes sels alcalins : le sulfate de potassium (K2SO4), le nitrate de potassium, le fluorure de potassium et d'aluminium (= la cryolithe de potassium ; (K3AIF6)), le tartrate de potassium hydrogéné, comme additifs anti-lueurs (voir les enseignements du brevet US 3 960 621 et de la demande de brevet EP 0 219 431) ; the use of potassium cryolite (K 3 AIF 6 ) as a combustion catalyst and that of alkaline salts, such as potassium sulphate (K 2 SO 4 ), potassium nitrate, potassium fluoride and aluminum fluoride; (= potassium cryolite (K 3 AIF 6 )), hydrogenated potassium tartrate, as anti-glare additives (see US Patent 4,381,270); the use of these same alkaline salts: potassium sulphate (K 2 SO 4 ), potassium nitrate, potassium and aluminum fluoride (potassium cryolite, (K 3 AlF 6 )), tartrate of hydrogenated potassium, as anti-glare additives (see the teachings of US Patent 3,960,621 and EP 0 219 431);
- l'utilisation de cryolite de potassium (K3AIF6), comme co-catalyseur (voir l'enseignement de la demande de brevet GB 2 258 230). the use of potassium cryolite (K 3 AIF 6 ) as a cocatalyst (see the teaching of patent application GB 2,258,230).
La demande de brevet US 2011/0284140 décrit l'éventuelle présence d'additifs anti-lueurs (notamment choisis parmi une cryolite, l'oxalate de sodium, le sulfate de potassium, le nitrate de potassium, un autre sel de potassium et leurs mélanges) dans des compositions double-base composites pour armes à tubes (armes légères). Lesdites compositions renferment typiquement essentiellement des charges énergétiques, de la nitrocellulose, du butyrate d'acétate de cellulose, un plastifiant énergétique et des additifs. Elles sont susceptibles de renfermer en outre au moins un liant supplémentaire, énergétique tel que le polyazoture de glycidyle (PAG ; non réticulé) ou non énergétique tel que le polybutadiène à fonctions hydroxyle terminales (PBHT). The patent application US 2011/0284140 describes the possible presence of anti-glare additives (in particular chosen from a cryolite, sodium oxalate, potassium sulphate, potassium nitrate, another potassium salt and their mixtures ) in composite double-base compositions for tube weapons (small arms). The compositions typically contain essentially energetic fillers, nitrocellulose, cellulose acetate butyrate, an energetic plasticizer, and additives. They may also contain at least one additional energetic binder such as glycidyl polyazide (PAG; non-crosslinked) or non-energetic such as polybutadiene with terminal hydroxyl functions (PBHT).
Les propergols solides double base présentent toutefois des performances énergétiques plus modestes que celles des propergols composites développés dans un deuxième temps. Ont tout particulièrement été développés, notamment pour les missiles tactiques, des propergols composites de type Nitramite® et Azamite®. However, the double-base solid propellants have a more modest energy performance than the composite propellants developed in a second time. Especially developed for tactical missiles are composite propellants such as Nitramite ® and Azamite ® .
Les propergols composites de type Nitramite® renferment des charges énergétiques (de type RDX ou HMX) dans un liant réticulé (de type polyester, polyéther ou polycaprolactone), plastifié avec de la nitroglycérine. En référence au problème technique de leur discrétion, leur
composition a été optimisée en ce qu'elle ne renferme pas de charges métalliques (telles des charges d'aluminium) aptes à générer des fumées primaires, pas ou peu de charges énergétiques inorganiques (telles des charges de perchlorate d'ammonium) aptes à générer des fumées secondaires et en ce qu'elle renferme des agents anti-leurs efficaces aptes à minimiser, voire supprimer les phénomènes de post combustion (on note incidemment ici que les nature et quantité d'agents anti-lueurs sont à optimiser dans la mesure où lesdits agents anti-lueurs sont susceptibles de générer des fumées primaires et/ou secondaires). A titre d'agents anti-lueurs efficaces, il a été proposé des composés à base de métaux alcalins, sodium (Na2S04,...) et surtout potassium (K2SO4, KNO3, K3AIF6, ...)■ A ce propos, on peut se référer à l'enseignement du livre « Technologie des propergols solides » par Alain DAVENAS (Editeur Masson), 1988, page 549. Des résultats très satisfaisants ont ainsi été obtenus (notamment avec utilisation de K2SO4, comme agent anti-lueur) dans les conditions d'utilisation de ces propergols composites de type Nitramite® (pressions de tir jusqu'à 10-12 MPa, en phase dite d'accélération). Composite propellants of Nitramite ® type contain energetic charges (of the RDX or HMX type) in a crosslinked binder (of polyester, polyether or polycaprolactone type), plasticized with nitroglycerine. In reference to the technical problem of their discretion, their composition has been optimized in that it does not contain metal charges (such as aluminum charges) able to generate primary fumes, no or little inorganic energy charges (such as ammonium perchlorate charges) capable of generating secondary fumes and in that it contains effective anti-their agents capable of minimizing or even eliminate the phenomena of post combustion (it is noted here incidentally that the nature and quantity of anti-light agents are to be optimized insofar as said anti-glare agents are capable of generating primary and / or secondary fumes). As effective anti-light agents, it has been proposed compounds based on alkali metals, sodium (Na 2 SO 4, ...) and especially potassium (K 2 SO 4, KNO 3 , K 3 AIF 6 , etc.). In this regard, reference can be made to the teaching of the book "Technology of solid propellants" by Alain DAVENAS (Masson), 1988, page 549. Very satisfactory results have thus been obtained (in particular with the use of K2SO4, as agent anti-glare) under the conditions of use of these composite propellants Nitramite ® type (firing pressures up to 10-12 MPa, in so-called acceleration phase).
Les propergols composites de type Azamite®sont des propergols encore plus énergétiques que ceux de type Nitramite®. Ils renferment des charges énergétiques (de type RDX ou HMX) dans un liant énergétique réticulé (de type polyazoture de glycidyle (PAG)), plastifié avec au moins un plastifiant énergétique. Ils sont opportunément utilisés jusqu'à des pressions de tir de l'ordre de 16 MPa, en phase dite d'accélération. Dans de telles conditions, les agents anti-lueurs de l'art antérieur (voir ci-dessus) se sont révélés inefficaces (pour notamment réduire de façon substantielle le phénomène de post combustion ; plus généralement en référence au problème technique de la discrétion). Les inventeurs ont tout
particulièrement mis en évidence (au sein donc de propergols de type Azamite®) l'inefficacité de K2SO4 (d5o = 285 μπι) conventionnellement utilisé au sein des propergols de type Nitramite®. Ils ont testé (au sein de propergols de type Azamite®) ce même agent anti-lueur de l'art antérieur, en l'utilisant à plus faible granulométrie (d5o = 15 μητι). Ils ont alors constaté que le phénomène de post combustion demeurait, malgré une amélioration sensible de la transmission dans le visible. Ils ont constaté qu'une flamme de post combustion était toujours présente (voir l'exemple comparatif C2 ci-après ainsi que la figure 1 annexée). L'homme du métier conçoit parfaitement que, dans un tel contexte, d'utilisation d'un propergol plus énergétique (Azamite®/Nitramite®) avec volonté d'optimiser les performances du moteur (pression en phase d'accélération : jusqu'à 16 MPa/10-12 MPa)), les problèmes de post combustion sont exacerbés. Il conçoit parfaitement que le problème technique de la discrétion est plus difficile à gérer. Composite propellants of the Azamite ® type are even more energetic propellants than those of the Nitramite ® type. They contain energetic charges (of the RDX or HMX type) in a crosslinked energy binder (of the glycidyl polyazide type (PAG)), plasticized with at least one energetic plasticizer. They are opportunely used up to firing pressures of the order of 16 MPa, in so-called acceleration phase. Under such conditions, the anti-light agents of the prior art (see above) have proved to be ineffective (in particular to substantially reduce the post-combustion phenomenon, more generally with reference to the technical problem of discretion). The inventors have everything particularly highlighted (thus within Azamite ® type propellants) the inefficiency of K2SO4 (d 5 o = 285 μπι) conventionally used in Nitramite ® type propellants. They tested (within Azamite ® type propellants) this same anti-glare agent of the prior art, using it at a smaller particle size (d 5 o = 15 μητι). They then found that the post-combustion phenomenon remained, despite a noticeable improvement in visible transmission. They found that a post-combustion flame was still present (see comparative example C2 below and attached FIG. 1). The skilled person fully understands that, in such a context, use of a more energetic propellant (Azamite ® / Nitramite ® ) with the desire to optimize the engine performance (pressure during acceleration phase: up to 16 MPa / 10-12 MPa)), post combustion problems are exacerbated. He perfectly understands that the technical problem of discretion is more difficult to manage.
De manière générale, l'homme du métier conçoit que la discrétion d'un produit pyrotechnique composite est d'autant plus problématique que les performances énergétiques dudit produit pyrotechnique composite sont élevées. In general, those skilled in the art understand that the discretion of a composite pyrotechnic product is all the more problematic as the energy performance of said composite pyrotechnic product is high.
II est du mérite des inventeurs de proposer, dans un contexte particulier (de propergols très énergétiques, destinés à être mis en combustion à haute pression (en phase d'accélération)), des agents anti-lueurs efficaces (lesdits agents anti-lueurs sont présents conventionnellement dans la composition des propergols à l'état de poudres ; ils sont introduits, conventionnellement, à l'état de poudres, lors de la préparation desdits propergols). Il est du mérite des inventeurs de proposer un nouveau propergol composite à liant énergétique spécifique (liant = un polymère énergétique spécifique (de type polyazoture de
glycidyle (PAG) hydroxytéléchélique) réticulé avec au moins un polyisocyanate), renfermant au moins un agent anti-lueur spécifique dans sa composition. Ce nouveau propergol composite est performant sur le plan énergétique (il présente notamment une haute vitesse de combustion) et reste discret (même en phase d'accélération, à des pressions jusqu'à 16 MPa). It is the merit of the inventors to propose, in a particular context (high energy propellants, intended to be put into combustion at high pressure (during the acceleration phase)), effective anti-light agents (said anti-light agents are Conventionally present in the composition of propellants in the form of powders, they are introduced, conventionally, in the form of powders, during the preparation of said propellants). It is the merit of the inventors to propose a new composite propellant with a specific energetic binder (binder = a specific energetic polymer (polyazide type). glycidyl (PAG) hydroxytelechelic) crosslinked with at least one polyisocyanate), containing at least one specific anti-glare agent in its composition. This new composite propellant is energy efficient (in particular it has a high combustion rate) and remains discrete (even during the acceleration phase, at pressures up to 16 MPa).
Selon son premier objet, la présente invention concerne donc de nouveaux produits pyrotechniques composites, fortement énergétiques. Ils sont du type à liant énergétique réticulé renfermant des charges énergétiques organiques. Ils renferment, plus précisément, dans un liant plastifié, comprenant un polymère énergétique réticulé et au moins un plastifiant énergétique, des charges énergétiques organiques et au moins un agent anti-lueur de type sel de potassium. De façon caractéristique : According to its first object, the present invention thus relates to new composite pyrotechnic products, highly energetic. They are of the crosslinked energy binder type containing organic energy charges. They contain, more specifically, in a plasticized binder comprising a crosslinked energy polymer and at least one energetic plasticizer, organic energetic fillers and at least one anti-glow agent of the potassium salt type. Characteristically:
- ledit polymère énergétique réticulé consiste en un polyazoture de glycidyle (PAG), ayant une masse moléculaire moyenne en nombre said crosslinked energy polymer consists of a glycidyl polyazide (PAG) having a number-average molecular weight
( n) comprise entre 700 et 3000 g/mol, réticulé, via ses fonctions terminales hydroxyles, avec au moins un agent de réticulation de type polyisocyanate ; et (n) between 700 and 3000 g / mol, crosslinked via its terminal hydroxyl functions with at least one polyisocyanate crosslinking agent; and
- ledit au moins un agent anti-lueur de type sel de potassium est choisi parmi la cryolite de potassium (K3AIF6), le tartrate de potassium monobasique (C4H5KO6) et leurs mélanges. said at least one anti-glow agent of the potassium salt type is chosen from potassium cryolite (K3AIF 6 ), potassium monobasic tartrate (C4H5KO6) and mixtures thereof.
La structure des produits pyrotechniques composites de l'invention associe donc, de façon caractéristique, un liant spécifique (énergétique) et au moins un agent anti-lueur (de type sel de potassium) spécifique. The structure of the composite pyrotechnic products of the invention therefore typically associates a specific binder (energetic) and at least one specific anti-glare agent (potassium salt type).
La nature du liant (celle de son polymère précurseur (énergétique)) constitue donc l'un des éléments clés (de la composition) des produits pyrotechniques composites de l'invention. La nature du au
moins un agent anti-lueur (de type sel de potassium) présent constitue donc l'autre des éléments clés (de la composition) des produits pyrotechniques composites de l'invention. The nature of the binder (that of its precursor (energetic) polymer) therefore constitutes one of the key elements (of the composition) of the composite pyrotechnic products of the invention. The nature of the less an anti-glow agent (potassium salt type) present is therefore the other key elements (of the composition) of the composite pyrotechnic products of the invention.
Ledit au moins un agent anti-lueur présent dans la composition des produits pyrotechniques composites de l'invention consiste donc en la cryolite de potassium (= le fluorure de potassium et d'aluminium ; (K3AIF6)), le tartrate de potassium monobasique (C4H5KO6) (ledit tartrate de potassium monobasique consistant lui-même en le L-tartrate de potassium monobasique, le D-tartrate de potassium monobasique ou en un mélange de ces deux formes énantiomères ; il consiste avantageusement en le L-tartrate de potassium monobasique (moins onéreux que le D-tartrate de potassium monobasique)) ou un de leurs mélanges. Il consiste avantageusement en la cryolite de potassium (K3AIF6) ou en le tartrate de potassium monobasique (C4H5KO6) (ledit tartrate de potassium monobasique consistant avantageusement en le L-tartrate de potassium monobasique (voir ci-dessus)). Il consiste très avantageusement en la cryolite de potassium (K3AIF6) (la signature en infra-rouge de ladite cryolite de potassium est plus discrète que celle dudit tartrate de potassium monobasique). Ces sels spécifiques de potassium, dont il est proposé, dans le cadre de l'invention, une utilisation originale (comme agents anti-lueurs pour propergols très énergétiques du type précisé (destinés à être mis en combustion à haute pression (en phase d'accélération))), sont des composés connus, disponibles commercialement, à des granulométries conventionnelles (poudres avec des grains présentant généralement un d5o entre 1 et 300 pm). Said at least one anti-glare agent present in the composition of the composite pyrotechnic products of the invention therefore consists of potassium cryolite (= potassium and aluminum fluoride (K 3 AIF 6 )), potassium tartrate monobasic (C4H5KO 6 ) (said monobasic potassium tartrate itself consisting of monobasic potassium L-tartrate, monobasic potassium D-tartrate or a mixture of these two enantiomeric forms, it advantageously consists of L-tartrate of monobasic potassium (less expensive than potassium d-tartrate monobasic)) or a mixture thereof. It consists advantageously of potassium cryolite (K 3 AIF 6 ) or of monobasic potassium tartrate (C 4 H 5 KO 6 ) (said monobasic potassium tartrate advantageously consisting of monobasic potassium L-tartrate (see above)) . It consists very advantageously of potassium cryolite (K 3 AIF 6 ) (the infra-red signature of said potassium cryolite is more discrete than that of said monobasic potassium tartrate). These specific potassium salts, which are proposed, in the context of the invention, an original use (as anti-glare agents for high energy propellants of the specified type (intended to be put into combustion at high pressure (in phase). acceleration))), are known compounds, commercially available, in conventional particle sizes (generally powders with grains having a d 5 o between 1 and 300 pm).
Ledit au moins un agent anti-lueur original est évidemment opportunément présent en une quantité efficace mais non excessive (le(s) sel(s) de potassium ajouté(s) convenant pour minimiser le phénomène de
post combustion mais étant susceptible(s) de générer des fumées primaires et, en tout état de cause, influant, de façon négative, sur le pouvoir énergétique). Cette quantité efficace et non excessive est généralement telle qu'elle assure dans la composition du produit une teneur en potassium de 0,2 à 5 % en masse, avantageusement de 0,2 à 2,5 % en masse. Cette teneur avantageuse en potassium de 0,2 à 2,5 % en masse correspond environ à une teneur massique, en l'un et/ou l'autre desdits sels spécifiques de potassium, de 1 à 5 %. On conçoit qu'à teneur équivalente en potassium recherchée, la teneur en dHsKOe requise est supérieure à celle requise en K3AIF6. Said at least one original anti-glare agent is obviously conveniently present in an effective amount but not excessive (the (s) added potassium salt (s) suitable for minimizing the phenomenon of post combustion but likely to generate primary fumes and, in any case, have a negative influence on the energy output). This effective and non-excessive amount is generally such that it provides in the composition of the product a potassium content of 0.2 to 5% by weight, preferably 0.2 to 2.5% by weight. This advantageous potassium content of 0.2 to 2.5% by weight corresponds approximately to a mass content, in one and / or the other of said specific potassium salts, of 1 to 5%. It is conceivable that at the desired potassium equivalent content, the required dHsKOe content is higher than that required in K3AIF6.
En référence à la nature du liant (liant énergétique donc), plus particulièrement à celle de son polymère précurseur (polyazoture de glycidyle hydroxytéléchélique), on peut ajouter ce qui suit. With reference to the nature of the binder (energy binder, therefore), more particularly to that of its precursor polymer (hydroxytelechelic glycidyl polyazide), the following can be added.
Notons tout d'abord que le « un » polyazoture de glycidyle doit se lire « au moins un » polyazoture de glycidyle dans tout le présent texte. En effet, il est nullement exclu du cadre de l'invention qu'un mélange d'au moins deux polyazotures de glycidyle (présentant des masses moléculaires (entre 700 et 3000 g/mol) et/ou des taux de ramification différents) soit utilisé comme polymère précurseur du liant des produits de l'invention. Note first that the "one" glycidyl polyazide should read "at least one" glycidyl polyazide throughout the present text. Indeed, it is in no way excluded from the scope of the invention to use a mixture of at least two glycidyl polyazides (having molecular weights (between 700 and 3000 g / mol) and / or different branching ratios). as precursor polymer of the binder of the products of the invention.
Le polymère énergétique précurseur du liant des produits de l'invention est donc un polyazoture, un polyazoture de glycidyle (PAG) qui présente des fonctions terminales hydroxy (un PAG hydroxytéléchélique) ; d'où 1) ses propriétés énergétiques et 2) sa capacité à être réticulé avec les agents de réticulation de type polyisocyanate. The precursor energy polymer of the binder of the products of the invention is therefore a polyazide, a glycidyl polyazide (PAG) which has terminal hydroxy functions (a hydroxytelechelic PAG); hence 1) its energetic properties and 2) its ability to be crosslinked with the polyisocyanate crosslinking agents.
Ledit polymère a une masse moléculaire adéquate (notamment, en référence à sa consistance (liquide) et à la consistance de son mélange avec essentiellement les charges (énergétiques organiques) et en
référence à la teneur relative du liant réticulé en agent(s) de réticulation), masse moléculaire moyenne en nombre (Mn) comprise entre 700 et 3000 g/mol, avantageusement entre 1700 et 2300 g/mol. Said polymer has an adequate molecular weight (in particular, with reference to its consistency (liquid) and the consistency of its mixture with essentially the (organic energy) charges and in particular reference to the relative content of the crosslinked binder in crosslinking agent (s)), a number-average molecular weight (Mn) of between 700 and 3000 g / mol, advantageously between 1700 and 2300 g / mol.
Les agents de réticulation, de type polyisocyanate (au moins bifonctionnels), convenant à la réticulation d'un tel polyazoture de glycidyle (PAG) hydroxytéléchélique sont connus per se. Il peut notamment s'agir de di- ou triisocyanates. Il s'agit avantageusement de polyisocyanates, liquides, choisis parmi le toluène diisocyanate (TDI), l'isophorone diisocyanate (IPDI), le dicyclohexyl méthylène diisocyanate (MDCI), l'hexaméthylène diisocyanate (HDI), le trimère dudit hexaméthylène diisocyanate (notamment commercialisé par la société Bayer sous la dénomination commerciale Desmodur® N 3300), le biuret trihexane isocyanate (BTHI), le S^^-triméthyl-l^-hexaméthylène diisocyanate et leurs mélanges. De façon particulièrement préférée, on utilise le trimère de l'hexaméthylène diisocyanate. Crosslinking agents, of the polyisocyanate type (at least bifunctional), which are suitable for the crosslinking of such a hydroxytelechelic glycidyl polyazide (PAG), are known per se. It may especially be di- or triisocyanates. These are advantageously liquid polyisocyanates chosen from toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), dicyclohexyl methylene diisocyanate (MDCl), hexamethylene diisocyanate (HDI), trimer of said hexamethylene diisocyanate (especially marketed by Bayer under the trade name Desmodur ® N 3300), biuret trihexane isocyanate (BTHI), the S ^^ - ^ -hexamethylene trimethyl-diisocyanate and mixtures thereof. In a particularly preferred manner, the trimer of hexamethylene diisocyanate is used.
Lesdits agents de réticulation sont conventionnellement utilisés en quantité nécessaire et suffisante, pour assurer la réticulation du polymère (non excessive pour ne pas polluer le produit réticulé obtenu). Ils sont conventionnellement utilisés en une quantité telle que le rapport de pontage (NCO (de l'agent de réticulation) /OH (du polymère)) soit compris entre 0,8 et 1,4, soit avantageusement de 1,2. Said crosslinking agents are conventionally used in an amount necessary and sufficient to ensure the crosslinking of the polymer (not excessive so as not to pollute the crosslinked product obtained). They are conventionally used in an amount such that the bridging ratio (NCO (of the crosslinking agent) / OH (of the polymer)) is between 0.8 and 1.4, or advantageously 1.2.
Le polymère énergétique réticulé représente généralement de 9 à 14 % en masse de la composition totale des produits pyrotechniques composites de l'invention. Le polymère énergétique per se est généralement intervenu pour 7 à 12 % en masse, le au moins un agent de réticulation pour environ 2 % en masse. The crosslinked energy polymer generally represents from 9 to 14% by weight of the total composition of the composite pyrotechnic products of the invention. The energy polymer per is generally involved for 7 to 12% by weight, the at least one crosslinking agent for about 2% by weight.
On a bien compris que la nature du liant (de son polymère précurseur) n'est pas per se originale mais que l'intérêt de l'invention
repose sur l'association d'un tel (polymère précurseur de) liant, énergétique, avec au moins un agent anti-lueur (de type sel de potassium) spécifique. It is understood that the nature of the binder (of its precursor polymer) is not per se original but that the interest of the invention is based on the combination of such an energetic binder precursor polymer with at least one specific anti-glare agent (potassium salt type).
De façon conventionnelle, au liant énergétique, est associé au moins un plastifiant énergétique. Le(s) plastifiants) énergétique(s) en cause est(sont) avantageusement de type nitrate et/ou nitramine. Le(s) plastifiant(s) énergétique(s) en cause est(sont) très avantageusement choisi(s) parmi le dinitrate de diéthylène glycol (DEGDN), le dinitrate de triéthylène glycol (TEGDN), le trinitrate de butanetriol (BTTN), le trinitrate de triméthyloléthane (TMETN), un mélange de 2,4-dinitro-2,4-diaza- pentane, de 2,4-dinitro-2,4-diaza-hexane et de 3,5-dinitro-3,5-diaza- heptane (et tout particulièrement le DNDA 5,7), les nitrato éthyl nitramines (notamment le méthyl-2-nitratoéthyl nitramine (méthylNENA) et réthyl-2-nitratoéthyl nitramine (éthylNENA)) et leurs mélanges. Conventionally, the energy binder is associated with at least one energetic plasticizer. The energy plasticizer (s) in question is (are) advantageously of the nitrate and / or nitramine type. The energy plasticizer (s) in question is (are) very advantageously selected from diethylene glycol dinitrate (DEGDN), triethylene glycol dinitrate (TEGDN), butanetriol trinitrate (BTTN) trimethylolethane trinitrate (TMETN), a mixture of 2,4-dinitro-2,4-diaza-pentane, 2,4-dinitro-2,4-diaza-hexane and 3,5-dinitro-3, 5-diaza-heptane (and especially DNDA 5.7), nitrato ethyl nitramines (especially methyl-2-nitratoethyl nitramine (methylNENA) and ethyl-2-nitratoethyl nitramine (ethylNENA)) and mixtures thereof.
Le(s) plastifiant(s) des produits pyrotechniques de l'invention représente(nt) généralement de 10 à 30 % en masse, plus généralement de 15 à 25 % en masse, de la composition totale desdits produits. The plasticizer (s) of the pyrotechnic products of the invention generally represent (s) from 10 to 30% by weight, more generally from 15 to 25% by weight, of the total composition of said products.
Les charges énergétiques présentes sont des charges organiques. The energy charges present are organic charges.
Les charges énergétiques organiques en cause ne sont pas per se originales. Il s'agit de charges énergétiques organiques connues perse et, pour la plupart, déjà conditionnées selon l'art antérieur dans des liants polymériques énergétiques réticulés (notamment de type PAG). Il s'agit avantageusement de charges d'hexogène (RDX), d'octogène (HMX), d'hexanitrohexaazaisowurtzitane (CL20), de nitroguanidine (NGU), d'éthylène dinitramine (EDNA), de dinitramide de N-guanylurée (FOX 12 (GUDN)), de l,l-diamino-2,2-dinitro éthylène (FOX 7 (DADE)), de 5,5'- azotétrazolate de bis(triaminoguanidinium) (TAGZT), de 5,5'-
azotétrazolate de dihydrazinium (DHDZT), de 5,5'-bis(tétrazolyl)hydrazine (HBT), de bis(2,2-dinitropropyl) nitramine (BDNPN), d'un nitropyrazole ou d'un mélange de ces charges (énergétiques organiques). The organic energy charges involved are not per se original. These are known organic energy charges Persian and, for the most part, already packaged according to the prior art in crosslinked energy polymer binders (in particular PAG type). It is advantageously charges of hexogen (RDX), octogen (HMX), hexanitrohexaazaisowurtzitane (CL20), nitroguanidine (NGU), ethylene dinitramine (EDNA), dinitramide N-guanylurea (FOX 12 (GUDN)), 1,1-diamino-2,2-dinitroethylene (FOX 7 (DADE)), 5,5'-azotetrazolate bis (triaminoguanidinium) (TAGZT), 5,5'- Dihydrazinium azotetrazolate (DHDZT), 5,5'-bis (tetrazolyl) hydrazine (HBT), bis (2,2-dinitropropyl) nitramine (BDNPN), a nitropyrazole or a mixture of these (energetic) organic).
Au sein des produits pyrotechniques composites de l'invention, on trouve donc un type de charge énergétique, avantageusement choisi parmi la liste ci-dessus, ou un mélange d'au moins deux types de charge énergétique, avantageusement choisis parmi la liste ci-dessus. Within the composite pyrotechnic products of the invention, there is therefore a type of energy charge, advantageously chosen from the list above, or a mixture of at least two types of energy charge, advantageously chosen from the list above. .
De façon préférée, on y trouve des charges énergétiques de RDX et/ou H MX, de façon plus préférée, des charges énergétiques de RDX ou de HMX. Preferably, there are energy charges of RDX and / or H MX, more preferably energy charges of RDX or HMX.
L'utilisation de charges d'hexogène et/ou de charges d'octogène est particulièrement préconisée dans la mesure où ces deux types de charges offrent un très satisfaisant compromis : sécurité/pouvoir énergétique et où il est aussi possible de mettre à profit, dans le cadre de l'invention, des acquis (résultant de l'utilisation de ces deux types de charges dans l'art antérieur). The use of hexogen charges and / or octogen charges is particularly recommended since these two types of charges offer a very satisfactory compromise: safety / energy efficiency and where it is also possible to take advantage of the scope of the invention, assets (resulting from the use of these two types of charges in the prior art).
Les charges énergétiques organiques se présentent conventionnellement sous la forme de grains solides, répartis de façon homogène au sein du liant réticulé plastifié. Ces grains solides présentent opportunément, de façon connue per se, plusieurs distributions granulométriques. Organic energy charges are conventionally in the form of solid grains, distributed homogeneously within the plasticized crosslinked binder. These solid grains suitably have, in a known manner per se, several particle size distributions.
Les charges énergétiques organiques des produits pyrotechniques de l'invention représentent généralement de 50 à 70 % en masse, plus généralement de 55 à 65 % en masse, de la composition totale desdits produits. On a compris que lesdits produits sont à fort taux de charge. The organic energy charges of the pyrotechnic products of the invention generally represent from 50 to 70% by weight, more generally from 55 to 65% by weight, of the total composition of said products. It is understood that said products are high load.
En référence à la discrétion recherchée, la présence de charges métalliques (d'aluminium, notamment), au sein du liant plastifié des
produits pyrotechniques de l'invention, est, elle, généralement exclue. De telles charges métalliques sont en effet susceptibles de générer des particules lors de leur combustion, i.e. de générer des fumées primaires. In reference to the desired discretion, the presence of metal charges (aluminum in particular), within the plasticized binder of pyrotechnic products of the invention, it is generally excluded. Such metal charges are indeed likely to generate particles during their combustion, ie to generate primary fumes.
La présence de charges énergétiques inorganiques (de perchlorate d'ammonium, notamment), au sein du liant plastifié des produits pyrotechniques de l'invention, n'est pas souhaitée mais ne saurait être totalement exclue. En tout état de cause, de telles charges énergétiques inorganiques, présentes, le sont obligatoirement, en référence à la discrétion recherchée, en faible quantité (< 4 % en masse). Elles peuvent être considérées comme des additifs (voir ci-après). Leur présence peut être opportune, en référence aux propriétés balistiques du produit. The presence of inorganic energy charges (of ammonium perchlorate, in particular) within the plasticized binder of the pyrotechnic products of the invention is not desired but can not be totally excluded. In any case, such inorganic energy charges, present, are necessarily, in reference to the discretion sought, in small quantities (<4% by weight). They can be considered as additives (see below). Their presence may be appropriate, with reference to the ballistic properties of the product.
Les produits pyrotechniques composites de l'invention sont par ailleurs susceptibles de renfermer, et renferment généralement, dans leur liant (polymère précurseur réticulé), outre les plastifia nt(s), charges énergétiques organiques et agent(s) anti-lueur spécifique(s), au moins un additif. On peut plus justement parler d'au moins un autre additif, les agents anti-lueur pouvant tout à fait s'analyser comme des additifs. Les agents anti-lueur ont été présentement isolés des autres additifs, dans la mesure où ils sont présents en référence au problème technique présentement considéré et où ils constituent donc un élément clé des produits de l'invention. The composite pyrotechnic products of the invention are moreover likely to contain, and generally contain, in their binder (crosslinked precursor polymer), in addition to plasticizers, organic energy charges and specific anti-glare agent (s). ), at least one additive. It is more apt to speak of at least one other additive, the anti-glare agents being quite capable of being analyzed as additives. The anti-glare agents have been presently isolated from the other additives, insofar as they are present with reference to the technical problem currently considered and where they therefore constitute a key element of the products of the invention.
Parmi les additifs opportunément présents, on privilégie les additifs conventionnels ci-après : les catalyseurs de réticulation, les agents de stabilisation du(des) plastifia nt(s) énergétique(s) présent(s) et les catalyseurs de combustion. Ainsi, selon une variante avantageuse, les produits pyrotechniques composites de l'invention renferment donc dans leur composition, outre le polymère (PAG) réticulé, les plastifiant(s),
charges énergétiques organiques et le au moins un agent anti-lueur spécifique, au moins un additif ; ledit au moins un additif comprenant au moins un catalyseur de réticulation et/ou au moins un agent de stabilisation du(des) plastifiant(s) présent(s) et/ou au moins un catalyseur de combustion. Ledit au moins un catalyseur de polymérisation peut notamment être choisi parmi le triphénylbismuth et le dibutyldilaurate d'étain (DBTL). Présent, il l'est généralement à une teneur ne dépassant pas 100 ppm. Ledit au moins un agent de stabilisation du(des) plastifiant(s) présents) peut notamment consister en au moins une aminé aromatique, telle la 2-nitrodiphénylamine (2-NDPA) et la N-méthylparanitroaniline (MNA). Présent, il l'est généralement à une teneur d'environ 1 % en masse. Ledit au moins un catalyseur de combustion peut notamment être choisi parmi les catalyseurs de combustion conventionnels, tels les sels et oxydes de plomb, et le citrate de bismuth. Ledit citrate de bismuth, en raison notamment de sa moindre toxicité, est préféré. La Demanderesse a décrit, dans la demande de brevet WO 2016/066245, l'utilisation avantageuse dudit citrate de bismuth comme catalyseur de combustion. Ledit au moins un catalyseur de combustion est généralement présent dans la composition des produits pyrotechniques de l'invention à un taux massique de 1 à 6 %, très généralement à un taux massique de 3 à 5 %. Among the additives that are suitably present, the following conventional additives are preferred: the crosslinking catalysts, the stabilizing agents of the plasticizer (s) energy (s) present (s) present and the combustion catalysts. Thus, according to an advantageous variant, the composite pyrotechnic products of the invention therefore contain in their composition, in addition to the crosslinked polymer (PAG), the plasticizers (s), organic energy charges and the at least one specific anti-glare agent, at least one additive; said at least one additive comprising at least one crosslinking catalyst and / or at least one stabilizing agent of the plasticizer (s) present (s) and / or at least one combustion catalyst. Said at least one polymerization catalyst may especially be chosen from triphenylbismuth and tin dibutyldilaurate (DBTL). Present, it is generally at a content not exceeding 100 ppm. Said at least one stabilizing agent for the plasticizer (s) present) may especially consist of at least one aromatic amine, such as 2-nitrodiphenylamine (2-NDPA) and N-methylparanitroaniline (MNA). Present, it is generally at a content of about 1% by weight. Said at least one combustion catalyst may especially be chosen from conventional combustion catalysts, such as lead salts and oxides, and bismuth citrate. Said bismuth citrate, especially because of its lower toxicity, is preferred. The Applicant has described, in the patent application WO 2016/066245, the advantageous use of said citrate of bismuth as a combustion catalyst. Said at least one combustion catalyst is generally present in the composition of the pyrotechnic products of the invention at a mass ratio of 1 to 6%, very generally at a mass ratio of 3 to 5%.
D'autres additifs susceptibles d'être présents dans la composition des produits pyrotechniques composites de l'invention peuvent notamment consister en des charges énergétiques inorganiques (voir ci-dessus) et en un ou plusieurs agents de mise en œuvre (auxiliaire(s) de fabrication). Le(s)dit(s) agent(s) est(sont) généralement présent(s) à une teneur de 1 à 2 % en masse.
Les additifs éventuellement présents (au vu des propos ci-dessus, on a compris que généralement plusieurs types d'additif sont présents) représentent généralement au maximum 10 % en masse de la composition des produits pyrotechniques composites de l'invention. Ils représentent très généralement de 0,1 à 10 % en masse (souvent de 1,5 à 10 % en masse) de la composition desdits produits pyrotechniques composites de l'invention. Other additives that may be present in the composition of the composite pyrotechnic products of the invention may especially consist of inorganic energetic charges (see above) and one or more implementing agents (auxiliaries). manufacturing). The said agent (s) is (are) generally present at a content of 1 to 2% by weight. The additives which may be present (in view of the above remarks, it has been understood that generally several types of additive are present) generally represent a maximum of 10% by weight of the composition of the composite pyrotechnic products of the invention. They generally represent from 0.1 to 10% by weight (often from 1.5 to 10% by weight) of the composition of said composite pyrotechnic products of the invention.
Au vu des propos ci-dessus, on comprend que les produits pyrotechniques composites de l'invention ne sont pas d'un type nouveau mais qu'ils sont nouveaux de par l'association, dans leur composition, d'un liant spécifique (PAG réticulé par au moins un polyisocyanate) et d'au moins un agent anti-lueur spécifique. In view of the above remarks, it is understood that the composite pyrotechnic products of the invention are not of a new type but that they are new by the combination, in their composition, of a specific binder (PAG crosslinked with at least one polyisocyanate) and at least one specific anti-glare agent.
Dans le cadre d'une variante avantageuse, la composition des produits pyrotechniques composites de l'invention, exprimée en pourcentages massiques, renferme donc : In the context of an advantageous variant, the composition of the composite pyrotechnic products of the invention, expressed in percentages by weight, thus contains:
- de 50 à 70 %, avantageusement de 55 à 65 %, de charges énergétiques organiques, et from 50 to 70%, advantageously from 55 to 65%, of organic energy charges, and
- de 9 à 14 % du polymère énergétique (de type PAG hydroxytéléchélique) réticulé {via ses fonctions terminales hydroxy par au moins un polyisocyanate), from 9% to 14% of the energy polymer (of the hydroxytelechelic PAG type) crosslinked (via its terminal hydroxy functions with at least one polyisocyanate),
- de 10 à 30 %, avantageusement de 15 à 25 %, d'au moins un plastifiant énergétique, from 10 to 30%, advantageously from 15 to 25%, of at least one energetic plasticizer,
- de 0 à 10 %, avantageusement de 0,1 à 10 %, d'au moins un additif, et from 0 to 10%, advantageously from 0.1 to 10%, of at least one additive, and
- ledit au moins un agent anti-lueur de type sel de potassium choisi parmi la cryolite de potassium (K3AIF6), le tartrate de potassium monobasique (QHSKOÔ) et leurs mélanges, en une quantité assurant une teneur en potassium dudit propergol de 0,2 % à 2,5 % en masse.
On comprend que les plages avantageuses indiquées ci-dessus peuvent tout à fait être considérées indépendamment les unes des autres. De préférence, elles le sont en combinaison les unes avec les autres. - said at least one antiglare potassium salt type selected from the potassium cryolite agent (K 3 AIF 6) monobasic potassium tartrate (QHSKO O) and mixtures thereof, in an amount ensuring a potassium content of said propellant from 0.2% to 2.5% by weight. It is understood that the advantageous ranges indicated above can quite be considered independently of each other. Preferably, they are in combination with each other.
Dans le cadre de cette variante avantageuse, ladite composition est généralement exempte de tout autre ingrédient (notamment de toute charge métallique) et consiste donc en les ingrédients listés ci-dessus, présents en les quantités indiquées ci-dessus. In the context of this advantageous variant, said composition is generally free of any other ingredient (especially any metallic filler) and therefore consists of the ingredients listed above, present in the amounts indicated above.
Le grand intérêt des produits de l'invention ressort à l'évidence des propos ci-dessus, The great interest of the products of the invention is evident from the above remarks,
On rappelle, à toutes fins utiles, que lesdits produits pyrotechniques composites conviennent notamment comme propergols solides pour chargements propulsifs de missiles tactiques. Leur utilisation à cette fin est particulièrement préconisée. Elle fait partie intégrante de la présente invention. It is recalled, for all practical purposes, that said composite pyrotechnic products are particularly suitable as solid propellants for propellant loading of tactical missiles. Their use for this purpose is particularly recommended. It is an integral part of the present invention.
La préparation desdits produits ne pose pas de difficultés particulières. Elle peut notamment être mise en œuvre par le procédé précisé ci-après, qui constitue un autre objet de l'invention. Il s'agit d'un procédé par analogie, qui, de façon caractéristique, fait intervenir le au moins un agent anti-lueur spécifique, dans la préparation d'un propergol avec liant de type PAG hydroxytéléchélique réticulé. The preparation of said products does not pose any particular difficulties. It can in particular be implemented by the method specified below, which constitutes another object of the invention. This is an analogous method, which typically involves the at least one specific anti-glare agent, in the preparation of a propellant with crosslinked hydroxytelechelic PAG binder.
La présente invention concerne donc aussi un procédé de préparation d'un produit pyrotechnique composite, tel que décrit ci- dessus. Ce procédé comprend : The present invention therefore also relates to a method for preparing a composite pyrotechnic product as described above. This process comprises:
- la constitution d'une pâte homogène par - the constitution of a homogeneous paste by
a) incorporation, avec agitation, à une température comprise entre 35 et 55°C, dans un polyazoture de glycidyle adéquat (PAG hydroxytéléchélique présentant une masse moléculaire en nombre telle que précisée ci-dessus), d'au moins un plastifiant énergétique, des
charges énergétiques organiques et des autres ingrédients constitutifs du produit pyrotechnique composite recherché (incluant le au moins un agent anti-lueur (de type sel de potassium) spécifique) à l'exception d'un quelconque agent de réticulation et d'un quelconque catalyseur de réticulation, et a) incorporation, with agitation, at a temperature of between 35 and 55 ° C., into a suitable glycidyl polyazide (hydroxytelechelic PAG having a number-average molecular weight as specified above), at least one energetic plasticizer, organic energy charges and other constitutive ingredients of the desired composite pyrotechnic product (including the at least one specific anti-glare (potassium salt type) agent) except for any crosslinking agent and any crosslinking, and
b) agitation du mélange résultant, sous vide partiel, à une (avantageusement ladite) température comprise entre 35 et 55°C ; b) stirring the resulting mixture, under partial vacuum, to a (preferably said) temperature of between 35 and 55 ° C;
- sous vide partiel, à une (avantageusement ladite) température comprise entre 35 et 55°C, l'incorporation, dans ladite pâte homogène constituée, d'éventuellement au moins un catalyseur de réticulation et, dudit au moins un agent de réticulation, suivie d'une agitation du mélange constitué ; under partial vacuum, at a temperature advantageously between 35 ° and 55 ° C., the incorporation into said homogeneous paste constituted of optionally at least one crosslinking catalyst and said at least one crosslinking agent, followed by agitation of the mixture formed;
- la coulée dudit mélange constitué (ayant été) agité (= du mélange obtenu) dans au moins une structure ; et pouring said mixture constituted (having been) stirred (= of the mixture obtained) into at least one structure; and
- le traitement thermique dudit mélange constitué (ayant été) agité coulé dans ladite au moins une structure. the heat treatment of said mixture constituted (having been) stirred in said at least one structure.
Le au moins un agent anti-lueur est introduit à l'état pulvérulent. The at least one anti-glare agent is introduced in powder form.
Le vide partiel mentionné est destiné au dégazage du milieu au-dessus duquel il est appliqué. Il est généralement de 10 mm Hg. On note incidemment qu'il n'est pas forcément d'intensité constante. The partial vacuum mentioned is intended for degassing of the medium above which it is applied. It is usually 10 mm Hg. Incidentally, it is not necessarily constant intensity.
Le traitement thermique (de réticulation (du PAG hydroxytéléchélique)) est généralement mis en œuvre à une température comprise entre 30 et 60°C (30°C < T < 60°C), pendant plusieurs jours. The heat treatment (crosslinking (of the hydroxytelechelic PAG)) is generally carried out at a temperature between 30 and 60 ° C (30 ° C <T <60 ° C) for several days.
On propose maintenant d'illustrer l'invention par les exemples et figures ci-après. On propose plus précisément deux exemples comparatifs (exemple comparatif Cl avec K2SO4 de forte granulométrie (dso = 285 pm), comme agent anti-lueur et exemple comparatif C2 avec
K2SO4 de faible granulométrie (d5o = 15 pm), comme agent anti-lueur) et deux exemples de l'invention (exemple 1 (avec K3AIF6 (dso * 30 pm), comme agent anti-lueur) et exemple 2 (avec C4H5KO6 (d5o ~ 50 pm), comme agent anti-lueur)). It is now proposed to illustrate the invention by the examples and figures below. More precisely, two comparative examples are proposed (comparative example C1 with K2SO4 of high particle size (dso = 285 μm), as anti-glare agent and comparative example C2 with K2SO4 of small particle size (d 5 o = 15 pm) as antiglare agent) and two examples of the invention (Example 1 (with K 3 AIF 6 (dso * 30 pm) as antiglare agent) and Example 2 (with C4H5KO6 (d 5 o ~ 50 pm) as antiglare agent)).
Les composés chimiques K2SO4, K3AIF6 et C4H5KO6 (L-tartrate de potassium monobasique) ont été obtenus auprès de la société SIGMA-ALDRICH. Chemical compounds K2SO4, K 3 AIF 6 and C4H5KO6 (potassium L-tartrate monobasic) were obtained from SIGMA-ALDRICH.
Les figures 1, 2 et 3 annexées représentent, pour chacun des propergols testés (respectivement celui de l'exemple comparatif C2 (avec K2SO4 (15 pm)), celui de l'exemple 1 et celui de l'exemple 2) les variations de la température (température de rayonnement équivalente corps noir (°C)) selon l'axe du jet (de gaz générés) en fonction de la distance (distance mesurée (en m) à partir de la sortie de la tuyère) ; le propergol testé l'étant à une pression de fonctionnement de 16 MPa (voir le point 5 ci-après). Les profils longitudinaux thermiques montrés ont été obtenus à l'aide de caméras IR sur la Bande II. Ces caméras ont permis de dresser un profil thermique bidimensionnel du jet émis par la tuyère. FIGS. 1, 2 and 3 show, for each of the propellants tested (respectively that of Comparative Example C2 (with K 2 SO 4 (15 pm)), that of Example 1 and that of Example 2). the temperature (equivalent black body radiation temperature (° C)) according to the axis of the jet (of generated gases) as a function of the distance (measured distance (in m) from the outlet of the nozzle); the propellant tested being at an operating pressure of 16 MPa (see point 5 below). The longitudinal thermal profiles shown were obtained using IR cameras on Band II. These cameras made it possible to draw a two-dimensional thermal profile of the jet emitted by the nozzle.
1. COMPOSITION MASSIQUE 1. MASS COMPOSITION
Les exemples 1 et 2 sont relatifs à des propergols selon l'invention comprenant, dans leur composition : Examples 1 and 2 relate to propellants according to the invention comprising, in their composition:
- des charges d'hexogène (RDX). La charge oxydante d'hexogène est conventionnelle : elle est constituées à 60 % en masse d'un RDX d'une classe granulométrique 0 - 100 pm et à 40 % en masse d'un RDX d'une classe granulométrique 2,5 pm - 5 pm ; - hexogen charges (RDX). The oxidizing charge of hexogen is conventional: it consists of 60% by weight of a RDX of a particle size class of 0 - 100 μm and 40% by weight of a RDX of a particle size class of 2.5 μm. 5 pm;
- un liant à base d'un polymère énergétique de type PAG hydroxytéléchélique (commercialisé par la société EURENCO (Mn (masse
moléculaire moyenne en nombre) = 1900 g/mol) réticulé (par le trimère de l'hexaméthylène diisocyanate commercialisé par la société Bayer sous la dénomination commerciale Desmodur® N 3300), plastifié par un mélange de deux plastifiants énergétiques (BTTN (trinitrate de butanediol)/TMETN (trinitrate de triméthyloléthane) : 50/50 (% massiques)) ; a binder based on an energetic polymer of the hydroxytelechelic PAG type (sold by the company EURENCO (Mn (mass Molecular number average) = 1900 g / mol) cross-linked (for the trimer of hexamethylene diisocyanate commercially available from Bayer under the trademark Desmodur ® N 3300), plasticized with a mixture of two energetic plasticizers (BTTN (trinitrate butanediol ) / TMETN (trimethylolethane trinitrate): 50/50 (mass%));
- des agents de stabilisation desdits plastifiants (NINA (N-méthylparanitroaniline)/2-NDPA (2-nitrodiphénylamine) ; 68/32 (% massiques)), agents for stabilizing said plasticizers (NINA (N-methylparanitroaniline) / 2-NDPA (2-nitrodiphenylamine) 68/32 (% by weight)),
- du citrate de bismuth en tant que catalyseur balistique ; et bismuth citrate as a ballistic catalyst; and
- un agent anti-lueur (K2AIF6 pour l'exemple 1 de l'invention et C4H5KO6 pour l'exemple 2 de l'invention). an anti-glare agent (K 2 AIF 6 for example 1 of the invention and C4H5KO6 for example 2 of the invention).
Lesdits propergols des exemples 1 et 2 de l'invention ont donc été comparés à des propergols (de composition similaire) renfermant K2SO4 à titre d'agent anti-lueur (les inventeurs ont donc testé l'utilisation, à titre d'agent anti-lueur, de K2SO4 dont le diamètre médian était de 285 pm et celle de K2S04 dont le diamètre médian était de 15 Mm. Dans les deux cas, ils ont observé une flamme de post combustion. La figure 1 montre les résultats obtenus avec le K2S04 de faible granulométrie (d50 = 15 pm) ; celle obtenue avec le K2SO4 de forte granulométrie (d5o = 285 m) était tout à fait similaire). Said propellants of Examples 1 and 2 of the invention were therefore compared with propellants (of similar composition) containing K2SO4 as an anti-glare agent (the inventors have therefore tested the use, as an anti-glare agent). of K2SO4 with a median diameter of 285 μm and that of K 2 SO 4 with a median diameter of 15 μm. In both cases, they observed a post-combustion flame. K 2 S0 4 of small particle size (d 50 = 15 pm) that obtained with the K 2 SO 4 of large particle size (d 5 o = 285 m) was quite similar).
Les agents anti-lueurs étaient présents, dans les compositions des propergols (des exemples comparatifs Cl et C2 et des exemples 1 et 2 de l'invention), à quasi iso-teneur (environ 0,9 % en masse) en potassium. The anti-glare agents were present in the propellant compositions (Comparative Examples C1 and C2 and Examples 1 and 2 of the invention), with almost iso-content (approximately 0.9% by weight) of potassium.
Les compositions massiques de chacun desdits propergols (qui comprennent en outre des auxiliaires de fabrication) sont indiquées dans le Tableau 1 ci-après. On peut plus précisément parler des compositions
massiques de la pâte précurseur de chacun desdits propergols (avant réticulation).
The mass compositions of each of said propellants (which further comprise manufacturing aids) are shown in Table 1 below. We can more precisely speak about compositions mass of the precursor paste of each of said propellants (before crosslinking).
2. MODE OPERATOIRE DE PREPARATION DES PATES DE PROPERGOL ET DES PROPERGOLS Dans un malaxeur, on a introduit le (polymère précurseur du liant = le) polyazoture de glycidyl (PAG) puis les plastifiants (BTTN/TMETN) et les agents de stabilisation (MNA/2-NDPA) desdits plastifiants. Le mélange a été malaxé durant 15 min à une température de 50°C. 2. PROCEDURE FOR THE PREPARATION OF PROPERGOL PASTES AND PROPERGOLS In a kneader, the (precursor polymer of the binder = a) glycidyl polyazide (PAG) was introduced followed by the plasticizers (BTTN / TMETN) and the stabilizing agents (MNA). / 2-NDPA) of said plasticizers. The mixture was kneaded for 15 minutes at a temperature of 50 ° C.
On a ensuite ajouté audit mélange, sous agitation, les charges énergétiques organiques (RDX), par portion, puis le catalyseur de combustion (citrate de bismuth), les additifs (autres que les agent et catalyseur de réticulation) et l'agent anti-lueur. L'agitation a alors été poursuivie pendant 2 h 30, à la température de 50°C et sous un vide de 10 mm de Hg (qui a permis le dégazage du milieu), pour l'obtention d'une pâte homogène. Then, with stirring, the organic energy charges (RDX) were added per portion, followed by the combustion catalyst (bismuth citrate), the additives (other than the crosslinking agent and catalyst) and the anti-corrosion agent. glow. Stirring was then continued for 2 h 30, at a temperature of 50 ° C. and under a vacuum of 10 mmHg (which allowed degassing of the medium), to obtain a homogeneous paste.
Le catalyseur de réticulation (DBTL (dibutyldilaurate d'étain) (55 ppm)) a alors été ajouté à ladite pâte homogène et le milieu a encore été agité 30 min avant l'addition de l'agent de réticulation du liant (Desmodur® N 3300). Ledit agent de réticulation a enfin été ajouté et le milieu a encore été agité 15 min (toujours à 50°C et sous vide). The crosslinking catalyst (DBTL (dibutyltin dilaurate) (55 ppm)) was then added to said homogeneous paste and the medium was further stirred 30 min before the addition of the binder crosslinking agent (Desmodur ® N 3300). Said crosslinking agent was finally added and the medium was stirred for 15 minutes (still at 50 ° C. and under vacuum).
On a ainsi préparé des lots de 800 g et des lots de 5 kg de pâte de propergol. Thus, 800 g batches and 5 kg batches of propellant paste were prepared.
Les lots de 800 g de pâte ont été en partie utilisés pour apprécier la faisabilité du procédé d'obtention des propergols (pour mesurer la vie de pot de la pâte) et en partie, après réticulation, pour évaluer le comportement balistique du propergol (pour mesurer la vitesse de combustion de celui-ci).
Les lots de 5 kg, partagés en deux, ont été réticulés. En fait, deux blocs de propergols (pour chacune des compositions) ont été préparés : deux blocs de diamètre 90 mm et de longueur 150 mm. Ils ont été testés (au banc d'essai : voir le point 5 ci-après). The batches of 800 g of pulp were partly used to assess the feasibility of the process of obtaining the propellants (to measure the pot life of the dough) and partly, after crosslinking, to evaluate the ballistic behavior of the propellant (for measure the burning rate of it). The batches of 5 kg, divided in two, were crosslinked. In fact, two blocks of propellants (for each of the compositions) were prepared: two blocks of diameter 90 mm and length 150 mm. They have been tested (on the test bench: see point 5 below).
Quelle que soit la pâte en cause, pour sa réticulation, elle a été coulée dans une structure adaptée puis soumise au traitement thermique ci-après : cuisson pendant 14 jours à une température de 50°C. Whatever the paste in question, for its crosslinking, it was cast in a suitable structure and then subjected to the following heat treatment: baking for 14 days at a temperature of 50 ° C.
3. DETERMINATION DE LA VIE DE POT DES PATES 3. DETERMINING THE PASTA LIFE OF PASTA
La vie de pot (qui permet d'apprécier la faisabilité du procédé d'obtention des propergols) a été déterminée par la mesure de la viscosité de la pâte de propergol en cause (renfermant l'agent de réticulation et le catalyseur de réticulation) au cours du temps, au moyen d'un viscosimètre Brookfield (avec le corps n°3 (mobile C) mis en rotation à 1 tour/min), à une température de 50°C. On a relevé le temps pour lequel la viscosité a atteint 15 kPo, afin de déterminer si le propergol répondait au critère d'industrialisation, c'est-à-dire si ledit temps relevé était supérieur à 10 h. 4. DETERMINATION DE LA VITESSE DE COMBUSTION DES PROPERGOLS The pot life (which makes it possible to assess the feasibility of the process for obtaining the propellants) was determined by measuring the viscosity of the propellant paste in question (containing the crosslinking agent and the crosslinking catalyst) at over time, using a Brookfield viscometer (with the body No. 3 (mobile C) rotated at 1 rpm), at a temperature of 50 ° C. The time for which the viscosity reached 15 kPo was recorded to determine if the propellant met the industrialization criterion, i.e. if the said time was greater than 10 h. 4. DETERMINATION OF COMBUSTION SPEED OF PROPERGOLS
La vitesse de combustion a été mesurée de façon conventionnelle à 20 °C et 10 MPa. The burning rate was measured conventionally at 20 ° C and 10 MPa.
Les résultats de vie de pot et de vitesse de combustion figurent dans le Tableau 2 ci-après.
Tableau 2 Pot life and burn rate results are shown in Table 2 below. Table 2
*Au vu des résultats de vie de pot indiqués, on voit que le critère d'industrialisation est largement satisfait. * Given the results of pot life indicated, we see that the criterion of industrialization is largely satisfied.
**On note que les agents anti-lueurs de l'invention ont tendance à abaisser la vitesse de combustion. Cela dépend bien évidemment, des quantités utilisées. Il est opportun de minimiser ces quantités pour conserver des vitesses de combustion supérieures à ** It is noted that the anti-glare agents of the invention tend to lower the rate of burning. This obviously depends on the quantities used. It is appropriate to minimize these quantities in order to maintain combustion speeds greater than
12 mm/s à 10 MPa. 12 mm / s to 10 MPa.
5. TESTS AU BANC D'ESSAI Des blocs obtenus ont été testés au banc d'essai dans des conditions de fonctionnement « sévères » : pression de tir égale à 16 MPa (ce qui correspond à la pression maximale de fonctionnement lors du tir, ce qui correspond à la pression lors de la phase dite d'accélération). 5. TESTS ON THE TEST BENCH Blocks obtained were tested on the test bench under "severe" operating conditions: firing pressure equal to 16 MPa (which corresponds to the maximum operating pressure during firing; which corresponds to the pressure during the so-called acceleration phase).
Pour vérifier la discrétion d'un moteur, on s'est volontairement placé à la pression de fonctionnement la plus élevée soit à, donc, 16 MPa (i.e. dans les conditions où cette discrétion est la plus difficile à gérer). To check the discretion of an engine, it was voluntarily placed at the highest operating pressure is, therefore, 16 MPa (i.e. under the conditions where this discretion is the most difficult to manage).
Certaines caractéristiques du jet (gaz émis en sortie de tuyère) ont été déterminées par des moyens optroniques, notamment par
observation par caméras IR en Bande II, par transmission/émission dans le visible (à 632 nm), et par transmission/émission dans l'IR entre 2 et 14 pm. Les profils longitudinaux thermiques obtenus par caméra IR (Bande II) permettent de mettre en évidence dans le jet des gradients en température équivalent corps noir. Les niveaux de transmission dans le visible et dans l'IR permettent de mettre en évidence la notion de transparence et donc l'efficacité des agents anti-lueurs testés. Some characteristics of the jet (gas emitted at the outlet of the nozzle) have been determined by optronic means, in particular by IR Band II observation, visible transmission / emission (at 632 nm), and transmission / emission in IR between 2 and 14 μm. The longitudinal thermal profiles obtained by IR camera (Band II) make it possible to highlight in the jet gradients in black body equivalent temperature. The levels of transmission in the visible and in the IR make it possible to highlight the notion of transparency and thus the effectiveness of the anti-light agents tested.
Sur les figures 1, 2 et 3 annexées, on a donc montré les résultats de l'observation par caméra IR (Bande II), i.e. les profils longitudinaux thermiques pour, respectivement, le propergol selon l'exemple comparatif C2 avec K2S04 (15 pm), le propergol selon l'exemple 1 de l'invention et le propergol selon l'exemple 2 de l'invention. In the appended FIGS. 1, 2 and 3, the results of the observation by IR camera (Band II) have thus been shown, ie the longitudinal thermal profiles for, respectively, the propellant according to Comparative Example C2 with K 2 SO 4. (15 pm), the propellant according to Example 1 of the invention and the propellant according to Example 2 of the invention.
Pour le propergol selon l'exemple comparatif C2, dont la composition contenait du K2SO4 (faible granulométrie), une flamme de post combustion était présente. Le niveau de rayonnement était élevé avec une température maximale équivalent corps noir de 1400°C, située à 1,2 m du plan de sortie de tuyère. La flamme de post combustion était parfaitement visible à l'œil nu. For the propellant according to Comparative Example C2, the composition of which contained K2SO4 (small particle size), a post combustion flame was present. The radiation level was high with a maximum blackbody equivalent temperature of 1400 ° C, located 1.2 m from the nozzle exit plane. The post combustion flame was perfectly visible to the naked eye.
Pour le propergol selon l'exemple 1 de l'invention, dont la composition contenait du K3AIF6, aucune flamme de post combustion n'a été décelée. Le jet a été considéré comme inerte. Le niveau de rayonnement en bande II est resté faible : la température maximale équivalent corps noir était de 600°C en sortie de tuyère (elle n'a pas dépassé cette valeur en s'éloignant du plan de sortie de ladite tuyère). For the propellant according to Example 1 of the invention, the composition of which contained K 3 AIF 6 , no post-combustion flame was detected. The jet was considered inert. The level of radiation in band II remained low: the maximum blackbody equivalent temperature was 600 ° C at the nozzle outlet (it did not exceed this value by moving away from the outlet plane of said nozzle).
Pour le propergol selon l'exemple 2 de l'invention, dont la composition contenait du C4H5KO6, de la même façon, aucune flamme de post combustion n'a été décelée. Le jet a été considéré comme inerte. Le niveau de rayonnement en bande II est resté faible : la température
maximale équivalent corps noir était de 650°C en sortie de tuyère (elle n'a pas dépassé cette valeur en s'éloignant du plan de sortie de ladite tuyère). Cette température maximale est un peu plus élevée que celle obtenue avec K3AIF6. For the propellant according to Example 2 of the invention, the composition of which contained C4H5KO6, in the same way, no post-combustion flame was detected. The jet was considered inert. The level of radiation in band II remained low: the temperature The maximum equivalent blackbody was 650 ° C at the nozzle outlet (it did not exceed this value by moving away from the exit plane of said nozzle). This maximum temperature is a little higher than that obtained with K 3 AIF 6 .
II n'a pas été observé, en présence de K3AIF6 (renfermant pourtant de l'aluminium) ou en présence de C4H5KO6, de fumées primaires (la transmission dans le visible à 632 nm était très élevée).
It was not observed, in the presence of K3AIF6 (containing however aluminum) or in the presence of C4H5KO6, primary fumes (the transmission in the visible at 632 nm was very high).
Claims
1. Produit pyrotechnique composite renfermant, dans un liant plastifié, comprenant un polymère énergétique réticulé et au moins un plastifiant énergétique, des charges énergétiques organiques et au moins un agent anti-lueur de type sel de potassium, caractérisé en ce que : 1. Composite pyrotechnic product comprising, in a plasticized binder, comprising a crosslinked energy polymer and at least one energetic plasticizer, organic energetic fillers and at least one potassium salt-type anti-glare agent, characterized in that:
- ledit polymère énergétique réticulé consiste en un polyazoture de glycidyle (PAG), ayant une masse moléculaire moyenne en nombre (Mn) comprise entre 700 et 3000 g/mol, réticulé, via ses fonctions terminales hydroxyles, avec au moins un agent de réticulation de type polyisocyanate ; et said crosslinked energy polymer consists of a glycidyl polyazide (PAG), having a number-average molecular weight (Mn) of between 700 and 3000 g / mol, crosslinked, via its hydroxyl terminal functions, with at least one crosslinking agent of polyisocyanate type; and
- ledit au moins un agent anti-lueur de type sel de potassium est choisi parmi la cryolite de potassium (K3AIF6), le tartrate de potassium monobasique (C4H5KO6) et leurs mélanges. said at least one anti-glare agent of potassium salt type is chosen from potassium cryolite (K3AIF6), potassium monobasic tartrate (C4H5KO6) and mixtures thereof.
2. Produit pyrotechnique composite selon la revendication 1, caractérisé en ce que ledit au moins un agent anti-lueur de type sel de potassium est présent en une quantité qui assure une teneur en potassium de 0,2 % à 2,5 % en masse. 2. Composite pyrotechnic product according to claim 1, characterized in that said at least one anti-glare agent of potassium salt type is present in an amount which assures a potassium content of 0.2% to 2.5% by weight. .
3. Produit pyrotechnique composite selon la revendication 1 ou 2, caractérisé en ce que ledit polyazoture de glycidyle (PAG) a une masse moléculaire en nombre (Mn) comprise entre 1700 et 2300 g/mol. 3. composite pyrotechnic product according to claim 1 or 2, characterized in that said glycidyl polyazide (PAG) has a number-average molecular weight (Mn) of between 1700 and 2300 g / mol.
4. Produit pyrotechnique composite selon l'une quelconque des revendications 1 à 3, caractérisé en ce que ledit au moins un plastifiant énergétique est de type nitrate et/ou nitramine.
4. Composite pyrotechnic product according to any one of claims 1 to 3, characterized in that said at least one energetic plasticizer is of the nitrate and / or nitramine type.
5. Produit pyrotechnique composite selon l'une quelconque des revendications 1 à 4, caractérisé en ce que lesdites charges énergétiques organiques sont choisies parmi les charges d'hexogène, les charges d'octogène, et les mélanges de telles charges. 5. Composite pyrotechnic product according to any one of claims 1 to 4, characterized in that said organic energy charges are selected from hexogen charges, octogen charges, and mixtures of such charges.
6. Produit pyrotechnique composite selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'il renferme en outre au moins un additif. 6. composite pyrotechnic product according to any one of claims 1 to 5, characterized in that it further contains at least one additive.
7. Produit pyrotechnique composite selon la revendication 6, caractérisé en ce que ledit au moins un additif est choisi parmi au moins un catalyseur de réticulation, au moins un agent de stabilisation du au moins un plastifiant énergétique, au moins un catalyseur de combustion et leurs mélanges. 7. composite pyrotechnic product according to claim 6, characterized in that said at least one additive is selected from at least one crosslinking catalyst, at least one stabilizing agent of the at least one energetic plasticizer, at least one combustion catalyst and their mixtures.
8. Produit pyrotechnique composite selon la revendication 6 ou 7, caractérisé en ce qu'il renferme du citrate de bismuth comme catalyseur de combustion. 8. Composite pyrotechnic product according to claim 6 or 7, characterized in that it contains bismuth citrate as a combustion catalyst.
9. Produit pyrotechnique composite selon l'une quelconque des revendications 1 à 8, caractérisé en ce que sa composition, exprimée en pourcentages massiques, renferme : 9. Composite pyrotechnic product according to any one of claims 1 to 8, characterized in that its composition, expressed in percentages by weight, contains:
- de 50 à 70 %, avantageusement de 55 à 65 %, desdites charges énergétique organiques, from 50 to 70%, advantageously from 55 to 65%, of said organic energy charges,
- de 9 à 14 % dudit polymère énergétique réticulé, from 9 to 14% of said crosslinked energy polymer,
- de 10 à 30 %, avantageusement de 15 à 25 %, dudit au moins un plastifiant énergétique,
- de 0 à 10 %, avantageusement de 0,1 à 10 %, d'au moins un additif ; et from 10 to 30%, advantageously from 15 to 25%, of said at least one energetic plasticizer, from 0 to 10%, advantageously from 0.1 to 10%, of at least one additive; and
- ledit au moins un agent anti-lueur de type sel de potassium choisi parmi la cryolite de potassium (K3AIF6), le tartrate de potassium monobasique (QHSKOÔ) et leurs mélanges, en une quantité assurant une teneur en potassium dudit propergol de 0,2 % à 2,5 % en masse. - said at least one antiglare potassium salt type selected from the potassium cryolite agent (K 3 AIF 6) monobasic potassium tartrate (QHSKO O) and mixtures thereof, in an amount ensuring a potassium content of said propellant from 0.2% to 2.5% by weight.
10. Produit pyrotechnique composite selon l'une quelconque des revendications 1 à 9, pour utilisation comme propergol solide d'un chargement propulsif d'un missile tactique. 10. Composite pyrotechnic product according to any one of claims 1 to 9, for use as a solid propellant of a propellant charge of a tactical missile.
11. Procédé de préparation d'un produit pyrotechnique composite selon l'une quelconque des revendications 1 à 10, caractérisé en ce qu'il comprend : 11. Process for preparing a composite pyrotechnic product according to any one of claims 1 to 10, characterized in that it comprises:
- la constitution d'une pâte homogène par - the constitution of a homogeneous paste by
a) incorporation, à une température comprise entre 35 et 55°C, dans ledit polyazoture de glycidyle, dudit au moins un plastifiant énergétique, des charges énergétiques organiques et des autres ingrédients constitutifs du produit pyrotechnique composite recherché à l'exception d'un quelconque agent de réticulation et d'un quelconque catalyseur de réticulation, et a) incorporation, at a temperature between 35 and 55 ° C, into said glycidyl polyazide, of said at least one energetic plasticizer, organic energy charges and other ingredients constituting the desired composite pyrotechnic product with the exception of any crosslinking agent and any crosslinking catalyst, and
b) agitation du mélange résultant, sous vide partiel, à une température comprise entre 35 et 55°C ; b) stirring the resulting mixture, under partial vacuum, at a temperature between 35 and 55 ° C;
- sous vide partiel, à une température comprise entre 35 et 55°C, l'incorporation, dans ladite pâte homogène constituée, d'éventuellement au moins un catalyseur de réticulation et, dudit au moins un agent de réticulation, suivie d'une agitation du mélange constitué ;
- la coulée dudit mélange constitué agité dans au moins une structure ; et under partial vacuum, at a temperature of between 35 ° and 55 ° C., the incorporation into said homogeneous paste constituted of optionally at least one crosslinking catalyst and said at least one crosslinking agent, followed by stirring; the mixture formed; pouring said stirred mixture into at least one structure; and
- le traitement thermique dudit mélange constitué agité coulé dans ladite au moins une structure.
the heat treatment of said stirred mixture formed in said at least one structure.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1601396A FR3056583B1 (en) | 2016-09-26 | 2016-09-26 | COMPOSITE PYROTECHNIC PRODUCT COMPRISING A POTASSIUM SALT-TYPE ANTI-LIGHT AGENT |
| PCT/FR2017/052573 WO2018055312A1 (en) | 2016-09-26 | 2017-09-25 | Composite pyrotechnic product containing an anti-gleam agent of potassium salt type |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3515881A1 true EP3515881A1 (en) | 2019-07-31 |
| EP3515881B1 EP3515881B1 (en) | 2021-02-17 |
Family
ID=58609440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP17787216.5A Active EP3515881B1 (en) | 2016-09-26 | 2017-09-25 | Composite pyrotechnic product containing an anti-gleam agent of potassium salt type |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP3515881B1 (en) |
| FR (1) | FR3056583B1 (en) |
| WO (1) | WO2018055312A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3096680B1 (en) | 2019-06-03 | 2021-09-24 | Arianegroup Sas | composite pyrotechnic product |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3960621A (en) * | 1957-03-12 | 1976-06-01 | Imperial Chemical Industries Limited | Propellents |
| SE7408998L (en) * | 1974-07-09 | 1976-01-12 | Bofors Ab | FLASH DAMPER FOR POWDER. |
| SE437511B (en) * | 1979-04-24 | 1985-03-04 | Bofors Ab | WANTED TO MAKE CONSOLIDATED BODY OF DOUBLE BASKET SHEETS |
| GB2258230B (en) | 1982-06-25 | 1993-10-13 | Poudres & Explosifs Ste Nale | Production of double-base propergol propellant blocks |
| FR2588551B1 (en) * | 1985-10-14 | 1987-11-20 | Poudres & Explosifs Ste Nale | PROCESS FOR PRODUCING A DOUBLE-BASED PROPULSIVE COMPOSITION WITH LOW FLAME LIGHT EMISSION, AND PROPULSIVE COMPOSITION THUS OBTAINED |
| DE102010020776B4 (en) * | 2010-05-18 | 2015-03-05 | Diehl Bgt Defence Gmbh & Co. Kg | Propellant charge and method for its production |
| FR3027597B1 (en) * | 2014-10-28 | 2016-12-09 | Herakles | PERFORMANT COMPOSITE PYROTECHNIC PRODUCT WITHOUT PB IN ITS COMPOSITION AND PREPARATION |
| DE102014016223B3 (en) | 2014-10-31 | 2016-02-18 | Audi Ag | Method for operating a communication system and communication system |
-
2016
- 2016-09-26 FR FR1601396A patent/FR3056583B1/en not_active Expired - Fee Related
-
2017
- 2017-09-25 EP EP17787216.5A patent/EP3515881B1/en active Active
- 2017-09-25 WO PCT/FR2017/052573 patent/WO2018055312A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018055312A1 (en) | 2018-03-29 |
| FR3056583A1 (en) | 2018-03-30 |
| FR3056583B1 (en) | 2018-10-19 |
| EP3515881B1 (en) | 2021-02-17 |
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