EP3212594A1 - PRODUIT PYROTECHNIQUE COMPOSITE PERFORMANT SANS Pb DANS SA COMPOSITION ET SA PREPARATION - Google Patents
PRODUIT PYROTECHNIQUE COMPOSITE PERFORMANT SANS Pb DANS SA COMPOSITION ET SA PREPARATIONInfo
- Publication number
- EP3212594A1 EP3212594A1 EP15808698.3A EP15808698A EP3212594A1 EP 3212594 A1 EP3212594 A1 EP 3212594A1 EP 15808698 A EP15808698 A EP 15808698A EP 3212594 A1 EP3212594 A1 EP 3212594A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composite pyrotechnic
- pyrotechnic product
- crosslinked
- product according
- catalyst
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 64
- 238000002485 combustion reaction Methods 0.000 claims abstract description 44
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- 239000011230 binding agent Substances 0.000 claims abstract description 32
- 239000004014 plasticizer Substances 0.000 claims abstract description 26
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 21
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 11
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 238000004132 cross linking Methods 0.000 claims description 24
- 239000000654 additive Substances 0.000 claims description 20
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 11
- 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 10
- 230000000996 additive effect Effects 0.000 claims description 9
- 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 8
- BSPUVYFGURDFHE-UHFFFAOYSA-N Nitramine Natural products CC1C(O)CCC2CCCNC12 BSPUVYFGURDFHE-UHFFFAOYSA-N 0.000 claims description 8
- 239000004615 ingredient Substances 0.000 claims description 8
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000010348 incorporation Methods 0.000 claims description 4
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 claims description 3
- -1 2,2-dinitropropyl Chemical group 0.000 claims description 3
- 239000000028 HMX Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- QCOXCILKVHKOGO-UHFFFAOYSA-N n-(2-nitramidoethyl)nitramide Chemical compound [O-][N+](=O)NCCN[N+]([O-])=O QCOXCILKVHKOGO-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- FXYYVODGZXUHLT-UHFFFAOYSA-N 2h-tetrazol-5-ylhydrazine Chemical compound NNC=1N=NNN=1 FXYYVODGZXUHLT-UHFFFAOYSA-N 0.000 claims description 2
- MZRUFMBFIKGOAL-UHFFFAOYSA-N 5-nitro-1h-pyrazole Chemical compound [O-][N+](=O)C1=CC=NN1 MZRUFMBFIKGOAL-UHFFFAOYSA-N 0.000 claims description 2
- NDYLCHGXSQOGMS-UHFFFAOYSA-N CL-20 Chemical compound [O-][N+](=O)N1C2N([N+]([O-])=O)C3N([N+](=O)[O-])C2N([N+]([O-])=O)C2N([N+]([O-])=O)C3N([N+]([O-])=O)C21 NDYLCHGXSQOGMS-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 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
- RSUBIPIJJJBPOU-UHFFFAOYSA-N NC(C(N(C(N(N)N)=N)N)([N+]([O-])=O)[N+]([O-])=O)(N)N(C(N(N)N)=N)N Chemical compound NC(C(N(C(N(N)N)=N)N)([N+]([O-])=O)[N+]([O-])=O)(N)N(C(N(N)N)=N)N RSUBIPIJJJBPOU-UHFFFAOYSA-N 0.000 claims 1
- ANERHPOLUMFRDC-UHFFFAOYSA-K bismuth citrate Chemical compound [Bi+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ANERHPOLUMFRDC-UHFFFAOYSA-K 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- FBUSEYSGCOSYEO-UHFFFAOYSA-N diaminomethylideneurea;nitramide Chemical compound N[N+]([O-])=O.N[N+]([O-])=O.NC(=N)NC(N)=O FBUSEYSGCOSYEO-UHFFFAOYSA-N 0.000 claims 1
- 150000001540 azides Chemical class 0.000 abstract 1
- 239000003380 propellant Substances 0.000 description 36
- 239000002243 precursor Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- 239000004449 solid propellant Substances 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000007787 solid Substances 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
- RUKISNQKOIKZGT-UHFFFAOYSA-N 2-nitrodiphenylamine Chemical compound [O-][N+](=O)C1=CC=CC=C1NC1=CC=CC=C1 RUKISNQKOIKZGT-UHFFFAOYSA-N 0.000 description 4
- HOQPTLCRWVZIQZ-UHFFFAOYSA-H bis[[2-(5-hydroxy-4,7-dioxo-1,3,2$l^{2}-dioxaplumbepan-5-yl)acetyl]oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HOQPTLCRWVZIQZ-UHFFFAOYSA-H 0.000 description 4
- 150000001621 bismuth Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 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 4
- REKWPXFKNZERAA-UHFFFAOYSA-K bismuth;2-carboxyphenolate Chemical compound [Bi+3].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O REKWPXFKNZERAA-UHFFFAOYSA-K 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920006037 cross link polymer Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- 102100025925 Oxysterol-binding protein-related protein 2 Human genes 0.000 description 2
- 101710201616 Oxysterol-binding protein-related protein 2 Proteins 0.000 description 2
- 235000013339 cereals Nutrition 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
- 150000002148 esters Chemical class 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
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229920005596 polymer binder Polymers 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
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 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
- 238000011144 upstream manufacturing Methods 0.000 description 2
- SQSPRWMERUQXNE-UHFFFAOYSA-N Guanylurea Chemical compound NC(=N)NC(N)=O SQSPRWMERUQXNE-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-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
- 239000002253 acid Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940036348 bismuth carbonate Drugs 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- GRBFCEINWFRDOG-UHFFFAOYSA-K di(octadecanoyloxy)bismuthanyl octadecanoate Chemical compound [Bi+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GRBFCEINWFRDOG-UHFFFAOYSA-K 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229960003711 glyceryl trinitrate Drugs 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
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 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
- XIFJZJPMHNUGRA-UHFFFAOYSA-N n-methyl-4-nitroaniline Chemical compound CNC1=CC=C([N+]([O-])=O)C=C1 XIFJZJPMHNUGRA-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
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 235000015927 pasta Nutrition 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- 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
-
- 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
- C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
Definitions
- the present invention relates to composite pyrotechnic products, particularly suitable as solid propellants for rocket engine propellant charges. It is more precisely composite pyrotechnic products, containing a high rate of organic energy charges in an energy binder. Said products are particularly interesting in that their composition does not contain lead, in that they are efficient, particularly in terms of the rate of combustion, and in that the pot life (see definition below) of their mixture precursor (before crosslinking) is high (their obtaining on an industrial scale is greatly facilitated).
- the binder is obtained from a liquid polymer
- the method currently used to manufacture such composite pyrotechnic products in the form of blocks is a batch process, called "batch", consisting in preparing a certain amount of paste, casting said quantity (at least a part of it). ci) in a number of structures (at least one) and heat treatment the (s) load (s) thus obtained (to crosslink the polymer).
- the various ingredients are therefore introduced in a proper order and carefully and long kneaded, under pressure conditions (usually under a partial vacuum) and temperature very precise.
- the mixture which is therefore in the form of a paste, is poured into at least one structure (said structure possibly being used with forming tools within it).
- the assembly then undergoes a heat treatment (baking) to ensure the crosslinking (hardening) of the polymer.
- the structure is in most cases the very envelope of the load.
- the introduction of the at least one crosslinking agent (and optionally at least one crosslinking catalyst) into the mixture is carried out towards the end of the kneading step. Indeed, as soon as said introduction, the dough - already persian more or less viscous, depending on the nature of the polymer, depending on the rate of charge ... - begins to crosslink (to "harden”). Thus, the casting can be done for a limited time, called “pot life", during which the mixture remains fluid enough to be poured. It is imperative, for an industrial implementation, that the pot life of the the paste is sufficiently high (in order to have the necessary time for the various casting operations).
- the pot life of a paste depends on the exact conditions (temperature and pressure) of casting said paste.
- the patent application FR 2 727 401 thus describes the use of bismuth salts, such as bismuth ⁇ -resorcylates, bismuth Y-resorylate, bismuth salicylate, bismuth citrate, bismuth stearate, and bismuth oxide, as combustion catalyst for double base solid propellants (nitrocellulose and at least one nitric ester such as nitroglycerine) or composite double base (fillers in an energetic binder based on a nitric ester).
- the use of these novel combustion catalysts has a disadvantage insofar as these are also found to be catalysts for crosslinking and where therefore their use reduces the pot life (see above).
- the Applicant proposes a new specific energy-binding composite propellant (comprising a specific energy polymer (PAG) crosslinked with at least one polyisocyanate), containing a specific combustion catalyst (bismuth citrate) in its composition.
- This new composite propellant whose composition does not contain lead, is energy efficient (it has a particular high speed of combustion) and its preparation process is particularly interesting.
- said crosslinked energy polymer consists of a glycidyl polyazide (PAG) having a number-average molecular weight
- binder precursor polymer The nature of the binder (that of its precursor polymer) is therefore one of the key elements (of the composition) of the composite pyrotechnic products of the invention.
- the energetic polymer selected as precursor 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 charges (organic energy) and with 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.
- binder of its precursor polymer
- advantage of the invention lies in the combination of such a (precursor polymer) binder with a catalyst of specific combustion.
- the energy charges present are organic charges.
- the organic energy charges involved are not per se original. These are organic energy charges known per se and, for the most part, already packaged according to the prior art in crosslinked energy polymer binders (in particular of the 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'-azotetrazolate of dihydrazinium (DHDZT), 5,5'-bis (tetrazolyl) hydrazine (HBT), bis (2,2-dinitropropyl) nitramine (BDNPN), a nitropyr
- 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.
- inorganic energy charges within the plasticized binder of the pyrotechnic products of the invention can not be totally excluded.
- inorganic energy charges present, are 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; however, it must not be responsible for the consequent formation of flue gases or flares.
- metal fillers within the plasticized binder of the pyrotechnic products of the invention, is, in turn, generally excluded. Such metal charges are indeed likely to generate particles during their combustion.
- combustion catalyst therefore constitutes the other of the key elements (of the composition) of the composite pyrotechnic products of the invention.
- Said combustion catalyst consists of bismuth citrate.
- Said bismuth citrate because of its lower toxicity, advantageously replaces the salts and lead oxides of the prior art.
- Bismuth citrate (the 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%.
- the composite pyrotechnic products of the invention are also likely to contain, and generally contain in their binder (crosslinked precursor polymer), besides the plasticizer (s), organic energy charges and combustion catalyst (specific), at least one additive . It is more apt to speak of at least one other additive, combustion catalysts generally constituting additives.
- the combustion catalysts have now been isolated from the other additives insofar as they are at the basis of the technical problem currently considered and where the combustion catalyst (specific) retained constitutes 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 combustion catalyst (bismuth citrate), at least an additive; said at least one additive comprising at least one crosslinking catalyst and / or at least one stabilizing agent for the plasticizer (s) present.
- Said at least one polymerization catalyst may especially be chosen from triphenylbismuth and dibutyldilaurate of tin (DBTL).
- Said at least one stabilizing agent of the plasticizer (s) present may in particular 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.
- 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 generally represent a maximum of 4% by weight of the composition of the composite pyrotechnic products of the invention. They represent very generally 0.1 to 4% 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 cross-linked by at least one polyisocyanate) and a specific combustion catalyst (bismuth citrate).
- a specific binder PAG cross-linked by at least one polyisocyanate
- a specific combustion catalyst bismuth citrate
- composition of the composite pyrotechnic products of the invention thus contains:
- 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.
- the great interest of the products of the invention is evident from the above remarks.
- the products are interesting per se (in terms of ballistic performance, also because of their mechanical properties, the weak signature of the generated plume (discretion) during their propellant combustion) and to the extent that the pot life of the dough (precursor ) containing the ingredients is similar to that of the paste of a similar propellant containing no bismuth citrate. More generally, the implementation of the preparation of the products of the invention is not difficult and is "optimized" in terms of temperature management.
- the present invention therefore relates to a method for preparing a composite pyrotechnic product, as described above.
- This process comprises: - the constitution of a homogeneous paste by
- 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 (of 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.
- This method may be considered as a method by analogy, but, typically, by the specific nature of the (binder precursor polymer) and the specific nature of the combustion catalyst, its first stages are carried out at temperatures (preferably a temperature) between 35 and 55 ° C (35 ° C ⁇ T (s) ⁇ 55 ° C) , (without cooling), without pot life problem (said polymer).
- Examples 1 and 2 relate to propellants according to the invention comprising, in their composition, hexogen (RDX) charges, a binder based on a hydroxytelechelic PAG type energy polymer (sold by the company EURENCO (Mn)).
- RDX hexogen
- Mn hydroxytelechelic PAG type energy polymer
- Example 1 Said propellants of Examples 1 and 2 were compared to reference propellants, for one (Ref.1) without ballistic catalyst in its composition (Example A) and for the other (Ref.2) with lead citrate. as a ballistic catalyst, in its composition, at a mass ratio of 1% (Example B1) and 3.5% (Example B2).
- Example 2 Two comparative examples are also presented with propellants similar to that of Example 2 according to the invention but comprising, as a ballistic catalyst, sub-salicylate of bismuth (Cl) and bismuth carbonate (C2), in place of bismuth citrate.
- sub-salicylate of bismuth (Cl) and bismuth carbonate (C2) in place of bismuth citrate.
- compositions of these propellants are presented in Table 1 below.
- RDX loads they consisted of 68% by weight of an RDX of a particle size class of 0 - 100 ⁇ and 32% by weight of an RDX with a particle size class of 2.5 - 5. ⁇ .
- Said Table 2 also contains, in its second part, combustion rate results measured at different pressures, on the finally obtained propellants.
- the (glycidyl polyazide precursor polymer) was introduced, then 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 40 ° C.
- the crosslinking catalyst (DBTL (55 ppm)) was then added to said homogeneous paste and the medium was further stirred 30 minutes before the addition of the crosslinking agent of the binder. Said crosslinking agent (Desmodur ® N 3300) was finally added and the medium was further stirred 15 min (still at 40 ° C and vacuum).
- each of the prepared propellant pastes was then poured into a suitable structure and then subjected to the following heat treatment: baking for 75 hours at a temperature of 50 ° C.
- the pot life was determined by measuring the viscosity of the propellant paste in question (containing the crosslinking agent and the crosslinking catalyst) over time, using a Brookfield viscometer (with the body). ° 3 (mobile C) rotated at 1 rpm) at a temperature of 40 ° 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 15 hours.
- the pastes of the reference propellants without a ballistic catalyst (example A) or containing lead citrate as a ballistic catalyst (examples B1 and B2) reached the (viscosity) value of 15 kPo beyond 24 hours, thus meeting the criterion of industrial flowability.
- the propellant paste of Example 1 (according to the invention) incorporating bismuth citrate at a mass content of 1% has properties of flowability equivalent to those of the reference propellants A (without ballistic catalyst) and B1 (containing 1% by weight of Pb citrate).
- Example 2 shows that, even at a high mass level (4%) of bismuth citrate, the propellant paste has maintained a viscosity of at least 15 kPo for at least 16 h, which is beyond the minimum time of 15 hours (required to industrially ensure the operations of casting the dough).
- Table 2 also shows that the ballistic catalyst (combustion catalyst), bismuth citrate, gives propellants according to the invention combustion rates, depending on the pressure, much higher than that of the reference propellant A (without a ballistic catalyst in its composition), and close to those of propellants B1 and B2 comprising, in their composition, lead citrate (toxic product) as a combustion catalyst.
- the ballistic catalyst combustion catalyst
- bismuth citrate bismuth citrate
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Abstract
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PL15808698T PL3212594T3 (pl) | 2014-10-28 | 2015-10-27 | Kompozytowy wyrób pirotechniczny o dużej efektywności, niezawierający w swojej kompozycji ołowiu i sposób jego wytwarzania |
Applications Claiming Priority (2)
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FR1402431A FR3027597B1 (fr) | 2014-10-28 | 2014-10-28 | Produit pyrotechnique composite performant sans pb dans sa composition et sa preparation |
PCT/FR2015/052888 WO2016066945A1 (fr) | 2014-10-28 | 2015-10-27 | PRODUIT PYROTECHNIQUE COMPOSITE PERFORMANT SANS Pb DANS SA COMPOSITION ET SA PREPARATION |
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EP3212594A1 true EP3212594A1 (fr) | 2017-09-06 |
EP3212594B1 EP3212594B1 (fr) | 2018-07-18 |
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EP15808698.3A Active EP3212594B1 (fr) | 2014-10-28 | 2015-10-27 | Produit pyrotechnique composite performant sans plomb dans sa composition et sa preparation |
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US (1) | US20180290945A1 (fr) |
EP (1) | EP3212594B1 (fr) |
JP (1) | JP6510640B2 (fr) |
KR (1) | KR102621576B1 (fr) |
FR (1) | FR3027597B1 (fr) |
IL (1) | IL251766B (fr) |
PL (1) | PL3212594T3 (fr) |
WO (1) | WO2016066945A1 (fr) |
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FR3056583B1 (fr) * | 2016-09-26 | 2018-10-19 | Airbus Safran Launchers Sas | Produit pyrotechnique composite renfermant un agent anti-lueur de type sel de potassium |
FR3090629B1 (fr) * | 2018-12-20 | 2021-07-23 | Arianegroup Sas | Procédé de préparation de produits pyrotechniques composites |
FR3096680B1 (fr) | 2019-06-03 | 2021-09-24 | Arianegroup Sas | produit pyrotechnique composite |
CN112500253B (zh) * | 2020-12-02 | 2022-04-12 | 湖北航天化学技术研究所 | 一种温敏时变高能固体推进剂 |
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US4268450A (en) * | 1977-08-08 | 1981-05-19 | Rockwell International Corporation | Energetic hydroxy-terminated azido polymer |
JPS63248791A (ja) * | 1987-04-06 | 1988-10-17 | 日本油脂株式会社 | 高エネルギ−バインダ型コンポジツト固体推進薬 |
FR2648809B1 (fr) * | 1989-06-21 | 1991-09-13 | Livbag Snc | Composition solide generatrice de gaz et son utilisation dans les generateurs de gaz pour coussins gonflables destines a proteger les passagers d'un vehicule automobile |
JPH075425B2 (ja) * | 1989-10-06 | 1995-01-25 | 防衛庁技術研究本部長 | ガス発生組成物 |
JPH07165483A (ja) * | 1993-12-13 | 1995-06-27 | Daicel Chem Ind Ltd | ガス発生剤組成物 |
FR2727401B1 (fr) * | 1994-11-29 | 1996-12-27 | Poudres & Explosifs Ste Nale | Compositions modificatrices de proprietes balistiques et propergols contenant de telles compositions |
US6183574B1 (en) * | 1999-09-02 | 2001-02-06 | The United States Of America As Represented By The Secretary Of The Army | Processing procedure for isocyanate cured propellants containing some bismuth compounds |
US6168677B1 (en) * | 1999-09-02 | 2001-01-02 | The United States Of America As Represented By The Secretary Of The Army | Minimum signature isocyanate cured propellants containing bismuth compounds as ballistic modifiers |
CA2351002C (fr) * | 2000-06-27 | 2009-04-07 | The Minister Of National Defence | Matieres explosives insensibles, obtenues par moulage a l'etat fondu, contenant des elastomeres thermoplastiques energetiques |
EP1186582A1 (fr) * | 2000-09-08 | 2002-03-13 | Her Majesty in Right of Canada, as represented by the Minister of National Defence | Composition de propergol insensibles contenant des élastomers thermoplastiques énergétiques à base de copolyuréthanes |
DE202004009449U1 (de) * | 2004-06-15 | 2004-10-28 | Trw Airbag Systems Gmbh | Gaserzeugende Zusammensetzung |
US8172965B2 (en) * | 2009-10-14 | 2012-05-08 | Raytheon Company | Explosive compositions and methods for fabricating explosive compositions |
DE102010020776B4 (de) * | 2010-05-18 | 2015-03-05 | Diehl Bgt Defence Gmbh & Co. Kg | Treibladung und Verfahren zu ihrer Herstellung |
GB2512346B (en) * | 2013-03-27 | 2021-06-30 | Bae Systems Plc | Non-phthalate propellants |
-
2014
- 2014-10-28 FR FR1402431A patent/FR3027597B1/fr active Active
-
2015
- 2015-10-27 PL PL15808698T patent/PL3212594T3/pl unknown
- 2015-10-27 KR KR1020177014380A patent/KR102621576B1/ko active IP Right Grant
- 2015-10-27 EP EP15808698.3A patent/EP3212594B1/fr active Active
- 2015-10-27 JP JP2017522927A patent/JP6510640B2/ja active Active
- 2015-10-27 US US15/522,608 patent/US20180290945A1/en not_active Abandoned
- 2015-10-27 WO PCT/FR2015/052888 patent/WO2016066945A1/fr active Application Filing
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Publication number | Publication date |
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IL251766A0 (en) | 2017-06-29 |
JP2017538648A (ja) | 2017-12-28 |
US20180290945A1 (en) | 2018-10-11 |
IL251766B (en) | 2020-04-30 |
EP3212594B1 (fr) | 2018-07-18 |
FR3027597A1 (fr) | 2016-04-29 |
JP6510640B2 (ja) | 2019-05-08 |
KR102621576B1 (ko) | 2024-01-05 |
WO2016066945A1 (fr) | 2016-05-06 |
FR3027597B1 (fr) | 2016-12-09 |
PL3212594T3 (pl) | 2019-01-31 |
KR20170101897A (ko) | 2017-09-06 |
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