EP3212594B1 - Efficient composite pyrotechnic product with no lead in the composition thereof and preparation of same - Google Patents
Efficient composite pyrotechnic product with no lead in the composition thereof and preparation of same Download PDFInfo
- Publication number
- EP3212594B1 EP3212594B1 EP15808698.3A EP15808698A EP3212594B1 EP 3212594 B1 EP3212594 B1 EP 3212594B1 EP 15808698 A EP15808698 A EP 15808698A EP 3212594 B1 EP3212594 B1 EP 3212594B1
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- EP
- European Patent Office
- Prior art keywords
- energetic
- composite pyrotechnic
- charges
- polymer
- pyrotechnic product
- 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.)
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Links
- 239000000203 mixture Substances 0.000 title claims description 60
- 239000002131 composite material Substances 0.000 title claims description 37
- 238000002360 preparation method Methods 0.000 title description 7
- 239000003054 catalyst Substances 0.000 claims description 64
- 238000002485 combustion reaction Methods 0.000 claims description 47
- 229920000642 polymer Polymers 0.000 claims description 39
- 239000011230 binding agent Substances 0.000 claims description 31
- 239000004014 plasticizer Substances 0.000 claims description 27
- 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 23
- 239000000654 additive Substances 0.000 claims description 23
- 230000000996 additive effect Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000005056 polyisocyanate Substances 0.000 claims description 12
- 229920001228 polyisocyanate Polymers 0.000 claims description 12
- 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 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000004615 ingredient Substances 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
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- -1 2,2-dinitropropyl Chemical group 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
- 239000000028 HMX Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- FUHQFAMVYDIUKL-UHFFFAOYSA-N fox-7 Chemical group NC(N)=C([N+]([O-])=O)[N+]([O-])=O FUHQFAMVYDIUKL-UHFFFAOYSA-N 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
- 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
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- JSOGDEOQBIUNTR-UHFFFAOYSA-N 2-(azidomethyl)oxirane Chemical compound [N-]=[N+]=NCC1CO1 JSOGDEOQBIUNTR-UHFFFAOYSA-N 0.000 claims 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- 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
- 239000003380 propellant Substances 0.000 description 37
- 238000004132 cross linking Methods 0.000 description 21
- 239000003431 cross linking reagent Substances 0.000 description 18
- 239000002243 precursor Substances 0.000 description 14
- 229910052797 bismuth Inorganic materials 0.000 description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 8
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 8
- 239000004449 solid propellant Substances 0.000 description 6
- 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 5
- RUKISNQKOIKZGT-UHFFFAOYSA-N 2-nitrodiphenylamine Chemical compound [O-][N+](=O)C1=CC=CC=C1NC1=CC=CC=C1 RUKISNQKOIKZGT-UHFFFAOYSA-N 0.000 description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- 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 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000010438 heat treatment 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
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000007787 solid Substances 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
- 238000013019 agitation Methods 0.000 description 4
- 150000001621 bismuth Chemical class 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 239000002245 particle Substances 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
- 238000001816 cooling Methods 0.000 description 3
- 229920006037 cross link polymer Polymers 0.000 description 3
- 229920005596 polymer binder 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
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229960001860 salicylate Drugs 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
- FXYYVODGZXUHLT-UHFFFAOYSA-N 2h-tetrazol-5-ylhydrazine Chemical compound NNC=1N=NNN=1 FXYYVODGZXUHLT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 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
- 241001080024 Telles Species 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
- 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
- AKAJRKUSJKGVFT-UHFFFAOYSA-K bismuth 2-carboxy-5-hydroxyphenolate Chemical compound [Bi+3].Oc1ccc(C([O-])=O)c(O)c1.Oc1ccc(C([O-])=O)c(O)c1.Oc1ccc(C([O-])=O)c(O)c1 AKAJRKUSJKGVFT-UHFFFAOYSA-K 0.000 description 1
- 229940036348 bismuth carbonate Drugs 0.000 description 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 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
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 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 patent application FR 2 727 401 thus describes the use of bismuth salts, such as bismuth ⁇ -resorcylates, bismuth ⁇ -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).
- bismuth salts such as bismuth ⁇ -resorcylates, bismuth ⁇ -resorylate, bismuth salicylate, bismuth citrate, bismuth stearate, and bismuth oxide
- 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.
- 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), nitrate ethyl nitramines (especially methyl-2-nitratoethyl nitramine (methylNENA) and ethyl-2-nitratoethyl nitramine (ethylNENA))
- 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.
- This method may be considered as a method by analogy, but, typically, by the specific nature of the (precursor polymer of) binder and the specific nature of the combustion catalyst, its first steps are carried out at temperatures (advantageously a temperature) between 35 and 55 ° C (35 ° C ⁇ T (s) ⁇ 55 ° C) , (without cooling), without pot life problem (said polymer).
- compositions of these propellants are presented in Table 1 below.
- 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Molecular Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
La présente invention concerne des produits pyrotechniques composites, convenant notamment comme propergols solides pour chargements propulsifs de moteurs de fusée. Il s'agit plus précisément de produits pyrotechniques composites, renfermant un fort taux de charges énergétiques organiques dans un liant énergétique. Lesdits produits sont particulièrement intéressants en ce que leur composition ne renferme pas de plomb, en ce qu'ils sont performants, notamment en termes de vitesse de combustion, et en ce que la vie de pot (voir définition ci-dessous) de leur mélange précurseur (avant réticulation) est élevée (leur obtention à l'échelle industrielle s'en trouve grandement facilitée).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).
Un propergol solide de type composite comprend des charges solides pulvérulentes (charges oxydantes, avec, éventuellement en sus, des charges réductrices) ainsi que divers additifs, notamment des additifs de faisabilité et des additifs de performance, dans un liant généralement plastifié (une matrice polymère solide - un polymère réticulé -, énergétique ou non, généralement plastifiée).A composite type solid propellant comprises pulverulent solid charges (oxidizing charges, with, optionally, reducing charges) and various additives, including feasibility additives and performance additives, in a generally plasticized binder (a polymer matrix). solid - a crosslinked polymer - energetic or not, usually plasticized).
Le liant est obtenu à partir d'un polymère liquide (« réticulable »), présentant des terminaisons chimiquement réactives, aptes à être réticulées par au moins un agent de réticulation (au moins bi-fonctionnel) lui aussi liquide. On introduit en fait généralement dans un tel polymère liquide, suivant un ordre approprié, au moins un plastifiant et les autres ingrédients du propergol, à l'exception dudit au moins un agent de réticulation (et d'au moins un catalyseur de réticulation, si un tel au moins un catalyseur de réticulation (généralement très sensible à l'humidité) est utilisé), puis finalement ledit au moins un agent de réticulation (et ledit éventuel au moins un catalyseur de réticulation utilisé). Le polymère chargé est alors traité thermiquement (« cuit ») à une température compatible avec les matériaux énergétiques (charges a minima) présents. Le polymère réticulé constitue, avec le(s) plastifiant(s) présent(s), le liant plastifié, qui enrobe tous les ingrédients et notamment les charges pulvérulentes, pour former finalement un corps solide.The binder is obtained from a liquid polymer ("crosslinkable") having chemically reactive terminations, capable of being crosslinked by at least one crosslinking agent (at least bi-functional) also liquid. At least one plasticizer and the other ingredients of the propellant, with the exception of the at least one crosslinking agent (and at least one crosslinking catalyst, if there is at least one plasticizer), are generally introduced into such a liquid polymer in an appropriate order. such at least one crosslinking catalyst (generally very sensitive to moisture) is used), then finally said at least one crosslinking agent (and said optional at least one crosslinking catalyst used). The polymer charged is then heat-treated ("cooked") at a temperature compatible with the energetic materials ( minimum loads) present. The crosslinked polymer constitutes, with the plasticizer (s) present (s), the plasticized binder, which coats all the ingredients and in particular the pulverulent fillers, to finally form a solid body.
Le procédé actuellement mis en oeuvre pour fabriquer de tels produits pyrotechniques composites sous la forme de blocs est un procédé discontinu, dit par "batch", consistant à préparer une certaine quantité de pâte, à couler ladite quantité (au moins une partie de celle-ci) dans un certain nombre de structures (au moins une) et à traiter thermiquement le(s) chargement(s) ainsi obtenu(s) (pour réticuler le polymère). Dans une première étape, les différents ingrédients sont donc introduits selon un ordre approprié puis soigneusement et longuement malaxés, dans des conditions de pression (en général, sous un vide partiel) et de température bien précises. Pour l'étape suivante, le mélange, qui se présente donc sous la forme d'une pâte, est coulé dans au moins une structure (ladite structure étant éventuellement utilisée avec des outillages de mise en forme en son sein). L'ensemble subit alors un traitement thermique (une cuisson) pour assurer la réticulation (le durcissement) du polymère. La structure constitue dans la plupart des cas l'enveloppe même du chargement.The process currently used to manufacture such composite pyrotechnic products in the form of blocks is a batch process, called "batch", consisting in preparing a certain quantity 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). In a first step, 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. For the next step, 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.
L'introduction du au moins un agent de réticulation (et de l'éventuel au moins un catalyseur de réticulation) dans le mélange se fait vers la fin de l'étape de malaxage. En effet, dès ladite introduction, la pâte - déjà per se plus ou moins visqueuse, selon la nature du polymère, selon le taux de charges ... - commence à réticuler (à « durcir »). Ainsi, la coulée ne peut se faire que durant un temps limité, dit « vie de pot », pendant lequel le mélange reste assez fluide pour être coulé. Il est impératif, pour une mise en oeuvre industrielle, que la vie de pot de la pâte soit suffisamment élevée (afin de disposer du temps nécessaire aux différentes opérations de coulée).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 per 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).
La vie de pot d'une pâte de propergol est évaluée par la mesure de l'évolution de la viscosité de ladite pâte au cours du temps. On considère qu'à partir d'une viscosité supérieure à 1,5 kPa.s = 15 kPo (15 kP), une pâte de propergol n'est plus « coulable », et qu'un temps inférieur à 15 h pour atteindre cette viscosité empêche toute industrialisation du procédé. Une viscosité de pâte inférieure ou égale à 1,5 kPa.s = 15 kPo au bout de 15 h est donc la condition (nécessaire et suffisante) qui assure la coulabilité de ladite pâte dans des conditions industrielles. L'homme du métier comprend bien évidemment que la vie de pot d'une pâte dépend des conditions exactes (de température et de pression) de coulée de ladite pâte.The pot life of a propellant paste is evaluated by measuring the evolution of the viscosity of said paste over time. It is considered that from a viscosity greater than 1.5 kPa.s = 15 kPo (15 kP), a propellant paste is no longer "flowable", and that a time less than 15 hours to reach this Viscosity prevents any industrialization of the process. A paste viscosity less than or equal to 1.5 kPa.s = 15 kPo after 15 hours is therefore the (necessary and sufficient) condition which ensures the flowability of said paste under industrial conditions. Those skilled in the art understand of course that the pot life of a paste depends on the exact conditions (temperature and pressure) of casting said paste.
Afin d'augmenter la vitesse de combustion d'un propergol solide, il est connu d'ajouter dans la composition dudit propergol solide des agents faisant fonction de catalyseur de combustion (on parle aussi de catalyseurs balistiques). Des sels organométalliques de plomb et des oxydes de plomb ont été utilisés à cette fin dans le passé. Le plomb, en raison de sa toxicité, a depuis été remplacé par le bismuth ; d'où l'utilisation de sels et d'oxydes de bismuth à titre de catalyseur de combustion de propergols solides.In order to increase the burning rate of a solid propellant, it is known to add in the composition of said solid propellant agents which act as combustion catalysts (also known as ballistic catalysts). Organometallic lead salts and lead oxides have been used for this purpose in the past. Lead, because of its toxicity, has since been replaced by bismuth; hence the use of salts and oxides of bismuth as a catalyst for burning solid propellants.
La demande de brevet
L'utilisation de ces nouveaux catalyseurs de combustion présente toutefois un inconvénient dans la mesure où ceux-ci se révèlent aussi des catalyseurs de la réticulation et où donc leur utilisation réduit la vie de pot (voir ci-dessus).The use of these novel combustion catalysts, however, 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).
Le brevet
Le brevet
A ce jour, l'homme du métier est toujours à la recherche d'un propergol performant, fortement énergétique, incorporant, dans sa composition, un catalyseur balistique non toxique (sans plomb), pouvant être obtenu, à l'échelle industrielle, avec une pâte présentant une vie de pot suffisamment longue et ce, dans des conditions de mise en oeuvre avantageuses, simples, notamment de gestion de la température.To date, the skilled person is still looking for a powerful propellant, highly energetic, incorporating, in its composition, a non-toxic ballistic catalyst (lead-free), which can be obtained, on an industrial scale, with a paste having a sufficiently long pot life and this under advantageous, simple operating conditions, in particular temperature management.
Dans un tel contexte, la Demanderesse propose un nouveau propergol composite à liant énergétique spécifique (comprenant un polymère énergétique spécifique (PAG) réticulé avec au moins un polyisocyanate), renfermant un catalyseur de combustion spécifique (du citrate de bismuth) dans sa composition. Ce nouveau propergol composite, dont la composition ne renferme pas de plomb, est performant sur le plan énergétique (il présente notamment une haute vitesse de combustion) et son procédé de préparation est particulièrement intéressant. Il est du mérite de la Demanderesse d'avoir sélectionné un couple, polymère précurseur de liant énergétique/catalyseur de combustion, qui, utilisé conventionnellement avec polyisocyanate(s), plastifiant(s) et charges énergétiques organiques, conduit à un propergol dont la pâte, avant réticulation, présente une vie de pot proche de celle d'un propergol similaire ne renfermant pas, dans sa composition, de catalyseur de combustion ou renfermant, dans sa composition, du citrate de plomb en tant que catalyseur de combustion ; et ce, à une température de 35-55°C (température, supérieure à la température ambiante, convenant parfaitement à une mise en oeuvre « simple » du procédé de préparation dudit propergol (voir ci-après)).In such a context, 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. It is the merit of the Applicant to have selected a pair, precursor polymer energy binder / combustion catalyst, which, conventionally used with polyisocyanate (s), plasticizer (s) and organic energy charges, leads to a propellant whose dough , before crosslinking, has a pot life close to that of a similar propellant does not contain, in its composition, combustion catalyst or containing, in its composition, lead citrate as a combustion catalyst; and this, at a temperature of 35-55 ° C (temperature, higher than room temperature, perfectly suitable for a "simple" implementation of the process for preparing said propellant (see below)).
Selon son premier objet, la présente invention concerne donc de nouveaux produits pyrotechniques composites, fortement énergétiques et ne renfermant pas de plomb dans leur composition. 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 un catalyseur de combustion. De façon caractéristique :
- 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
- le catalyseur de combustion consiste en le citrate de bismuth.
- 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 the type polyisocyanate; and
- the combustion catalyst consists of bismuth citrate.
La structure des produits pyrotechniques composites de l'invention associe donc, de façon caractéristique, un liant spécifique et un catalyseur de combustion spécifique. Cette association s'est révélée particulièrement avantageuse en référence au cahier des charges qui comporte deux stipulations a priori contradictoires (les catalyseurs de combustion se révélant généralement aussi des catalyseurs de réticulation (voir ci-dessus)) : hautes performances énergétiques (hautes vitesses de combustion) du produit (requérant la présence d'un catalyseur de combustion en quantité efficace) et gestion aisée de son procédé d'obtention (tout particulièrement en référence au problème de la durée de vie (de la « vie de pot ») de la pâte à réticuler).The structure of the composite pyrotechnic products of the invention therefore typically associates a specific binder and a specific combustion catalyst. This combination has proved to be particularly advantageous with reference to the specification which includes two stipulations that are a priori contradictory (combustion catalysts are generally also found as crosslinking catalysts (see above)): high energy performance (high combustion rates) ) of the product (requiring the presence of a combustion catalyst in an effective amount) and easy management of its production process (especially with reference to the problem of the life (of "pot life") of the dough to crosslink).
La nature du liant (celle de son polymère précurseur) constitue donc l'un des éléments clés (de la composition) des produits pyrotechniques composites de l'invention.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.
Notons incidemment ici que le « un » polyazoture de glycidyle (= polymère précurseur du liant) 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.Incidentally note here that the "a" glycidyl polyazide (= binder precursor polymer) 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 sélectionné comme 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 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.
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 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.
Il est du mérite des inventeurs d'avoir identifié (sélectionné) ce type (de polymère précurseur) de liant, convenant parfaitement pour utilisation avec du citrate de bismuth comme catalyseur de combustion.It is the merit of the inventors to have identified (selected) this type (precursor polymer) binder, suitable for use with bismuth citrate as a combustion catalyst.
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 dicyclohexylméthylène 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 3,5,5-triméthyl-1,6-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), dicyclohexylmethylene diisocyanate (MDCl), hexamethylene diisocyanate (HDI), trimer of said hexamethylene diisocyanate (in particular sold by the company Bayer under the trade name Desmodur® N 3300), biuret trihexane isocyanate (BTHI), 3,5,5-trimethyl-1,6-hexamethylene 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.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 of 1.
Le polymère énergétique réticulé représente généralement de 10 à 14 % en masse de la composition totale des produits pyrotechniques composites de l'invention. Le polymère énergétique per se est généralement intervenu pour 8 à 12 % en masse, le au moins un agent de réticulation pour environ 2 % en masse.The crosslinked energy polymer generally represents from 10 to 14% by weight of the total composition of the composite pyrotechnic products of the invention. The energy polymer per is generally involved for 8 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 avec un catalyseur de combustion spécifique.It is understood that the nature of the binder (of its precursor polymer) is not per se original but that the advantage of the invention lies in the combination of such a (precursor polymer) binder with a catalyst of specific combustion.
De façon conventionnelle, au liant énergétique, est associé au moins un plastifiant énergétique. Le(s) plastifiant(s) 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 l'éthyl-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), nitrate 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 per se 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 1,1-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 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-dinitro ethylene (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 nitropyrazole or a mixture of these fillers (organic energy ).
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. De façon préférée, on y trouve des charges énergétiques de RDX.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. . Preferably, there are energetic charges of RDX.
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.
La présence de charges énergétiques inorganiques, au sein du liant plastifié des produits pyrotechniques de l'invention, ne saurait être totalement exclue. En tout état de cause, de telles charges énergétiques inorganiques, présentes, le sont 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 ; elle ne doit toutefois pas être responsable de la formation conséquente de fumées ou lueurs de combustion.The presence of inorganic energy charges within the plasticized binder of the pyrotechnic products of the invention can not be totally excluded. In any case, such 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.
La présence de charges métalliques, au sein du liant plastifié des produits pyrotechniques de l'invention, est, quant à elle, généralement exclue. De telles charges métalliques sont en effet susceptibles de générer des particules lors de leur combustion.The presence of 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.
La nature du catalyseur de combustion présent constitue donc l'autre des éléments clés (de la composition) des produits pyrotechniques composites de l'invention. Ledit catalyseur de combustion consiste en le citrate de bismuth. Ledit citrate de bismuth, en raison de sa moindre toxicité, se substitue avantageusement aux sels et oxydes de plomb de l'art antérieur. De surcroit, de façon surprenante, ledit citrate de bismuth, catalyseur de combustion spécifique, au sein du liant plastifié spécifique des produits pyrotechniques de l'invention, exerce un effet positif sur la combustion (tout particulièrement sur la vitesse de combustion) sans poser de problème en amont lors de la préparation du produit (le procédé de préparation étant d'une mise en oeuvre « aisée », généralement « à température constante » jusqu'à la réticulation du polymère, en tout état de cause qui inclut aucun refroidissement substantiel (du type de celui décrit dans les brevets
Le citrate de bismuth (le 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 %.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%.
Les produits pyrotechniques composites de l'invention sont par ailleurs susceptibles de renfermer, et renferment généralement, dans leur liant (polymère précurseur réticulé), outre les plastifiant(s), charges énergétiques organiques et catalyseur de combustion (spécifique), au moins un additif. On peut plus justement parler d'au moins un autre additif, les catalyseurs de combustion constituant en général des additifs. Les catalyseurs de combustion ont été présentement isolés des autres additifs, dans la mesure où ils sont à la base du problème technique présentement considéré et où le catalyseur de combustion (spécifique) retenu constitue un élément clé des produits de l'invention.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.
Parmi les additifs opportunément présents, on privilégie les additifs conventionnels ci-après : les catalyseurs de réticulation et les agents de stabilisation du(des) plastifiant(s) énergétique(s) présent(s). 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 catalyseur de combustion (citrate de bismuth), 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). 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) présent(s) peut notamment consister en au moins une amine 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.Among the additives that are suitably present, the following conventional additives are preferred: the crosslinking catalysts and the stabilizing agents of the plasticizer (s) energy (s) present (s). 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 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). Present, it is generally at a content not exceeding 100 ppm. Said at least one stabilizing agent for 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.
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 oeuvre (auxiliaire(s) de fabrication). Le(s)dit(s) agent(s) est(sont) généralement présent(s) à une teneur de 1 à 2 % en masse.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 processing agents (auxiliaries). manufacturing). The said agent (s) is (are) generally present at a content of 1 to 2% by weight.
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 4 % en masse de la composition des produits pyrotechniques composites de l'invention. Ils représentent très généralement de 0,1 à 4 % en masse de la composition desdits produits pyrotechniques composites de l'invention.The additives that 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 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.
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'un catalyseur de combustion spécifique (le citrate de bismuth).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 cross-linked by at least one polyisocyanate) and a specific combustion catalyst (bismuth citrate).
Dans le cadre d'une variante avantageuse, la composition des produits pyrotechniques composites de l'invention, exprimée en pourcentages massiques, renferme donc :
- de 50 à 70 %, avantageusement de 55 à 65 %, de charges énergétiques organiques, et
- de 10 à 14 % du polymère énergétique (de type PAG hydroxytéléchélique) réticulé (via ses fonctions terminales hydroxy par au moins un polyisocyanate),
- de 10 à 30 %, avantageusement de 15 à 25 %, d'au moins un plastifiant énergétique,
- de 1 à 6 %, avantageusement 3 à 5 %, de citrate de bismuth, et
- de 0 à 4 %, avantageusement de 0,1 à 4 %, d'au moins un additif.
- from 50 to 70%, advantageously from 55 to 65%, of organic energy charges, and
- from 10 to 14% of the energy polymer (of the hydroxytelechelic PAG type) crosslinked ( via its terminal functions hydroxy with at least one polyisocyanate),
- from 10 to 30%, advantageously from 15 to 25%, of at least one energetic plasticizer,
- from 1 to 6%, advantageously 3 to 5%, of bismuth citrate, and
- from 0 to 4%, advantageously from 0.1 to 4%, of at least one additive.
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.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. Les produits sont intéressants per se (en termes de performances balistiques, de par aussi leurs propriétés mécaniques, la faible signature du panache généré (discrétion) lors de leur combustion en propulseur) et dans la mesure où la vie de pot de la pâte (précurseur) contenant les ingrédients est proche de celle de la pâte d'un propergol similaire ne renfermant pas de citrate de bismuth. Plus généralement, la mise en oeuvre de la préparation des produits de l'invention ne pose pas de difficulté et se révèle « optimisée » en terme de gestion de température.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.
Selon son second objet, la présente invention concerne donc un procédé de préparation d'un produit pyrotechnique composite, tel que décrit ci-dessus. Ce procédé comprend :
- la constitution d'une pâte homogène par
- 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 catalyseur de combustion spécifique : le citrate de bismuth) à l'exception d'un quelconque agent de réticulation et d'un quelconque catalyseur de réticulation, et
- b) agitation du mélange résultant, sous vide partiel, à une (avantageusement ladite) température comprise entre 35 et 55°C ;
- sous vide partiel, à une (avantageusement ladite) température comprise entre 35 et 55°C, l'incorporation, dans ladite pâte homogène constituée, dudit au moins un agent de réticulation et éventuellement d'au moins un catalyseur de réticulation, suivie d'une agitation du mélange constitué ;
- la coulée dudit mélange constitué (ayant été) agité (= du mélange obtenu) dans au moins une structure ; et
- le traitement thermique dudit mélange constitué (ayant été) agité coulé dans ladite au moins une structure.
- the constitution of a homogeneous paste by
- 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 specific combustion catalyst: bismuth citrate) with the exception of any crosslinking agent and any crosslinking catalyst, and
- b) stirring the resulting mixture, under partial vacuum, to a (preferably said) temperature of between 35 and 55 ° C;
- partial vacuum, at a (advantageously said) temperature between 35 and 55 ° C, the incorporation into said homogeneous paste consisting of said at least one crosslinking agent and optionally at least one crosslinking catalyst, followed by stirring the mixture formed;
- pouring said mixture formed (having been) stirred (= of the mixture obtained) into at least one structure; and
- the heat treatment of said mixture constituted (having been) agitated in said at least one structure.
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 oeuvre à une température comprise entre 30 et 60°C (30°C ≤ T ≤ 60°C), pendant plusieurs jours.The heat treatment (of crosslinking (of the hydroxytelechelic PAG)) is generally carried out at a temperature of between 30 and 60 ° C. (30 ° C. ≤ T ≤ 60 ° C.) for several days.
Ce procédé peut être considéré comme un procédé par analogie, mais, de façon caractéristique, de par la nature spécifique du (polymère précurseur du) liant et la nature spécifique du catalyseur de combustion, ses premières étapes sont mises en oeuvre à des températures (avantageusement une température) entre 35 et 55°C (35°C ≤ T(s) ≤ 55°C), (sans refroidissement), sans problème de vie de pot (dudit polymère).This method may be considered as a method by analogy, but, typically, by the specific nature of the (precursor polymer of) binder and the specific nature of the combustion catalyst, its first steps are carried out at temperatures (advantageously a temperature) between 35 and 55 ° C (35 ° C ≤ T (s) ≤ 55 ° C) , (without cooling), without pot life problem (said polymer).
On se propose maintenant d'illustrer l'invention par les exemples ci-après. On propose plus précisément ci-après les exemples A, B1 et B2, illustrant l'art antérieur, les exemples 1 et 2 illustrant l'invention et les exemples comparatifs C1 et C2.It is now proposed to illustrate the invention by the examples below. Examples A, B1 and B2, which illustrate the prior art, are more specifically described below, examples 1 and 2 illustrating the invention and comparative examples C1 and C2.
Les exemples 1 et 2 sont relatifs à des propergols selon l'invention comprenant, dans leur composition, des charges d'hexogène (RDX), 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/TMETN ; 30/70 (% massiques))), des agents de stabilisation desdits plastifiants (MNA/2-NDPA ; 75/25 (% massiques)) et du citrate de bismuth en tant que catalyseur balistique (à un taux massique de 1% pour l'exemple 1 et à un taux massique de 4 % pour l'exemple 2).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)). (number average molecular weight) = 1900 g / mol) crosslinked (by the trimer of hexamethylene diisocyanate marketed by Bayer under the trade name Desmodur® N 3300), plasticized (by a mixture of two energetic plasticizers (BTTN / TMETN; 30/70 (% by weight))), stabilizers of said plasticizers (MNA / 2-NDPA, 75/25 (% by weight)) and bismuth citrate as a ballistic catalyst (at a mass ratio of 1 % for Example 1 and at a mass ratio of 4% for Example 2).
Lesdits propergols des exemples 1 et 2 ont été comparés à des propergols de référence, pour l'un (Réf. 1) sans catalyseur balistique dans sa composition (exemple A) et pour l'autre (Réf. 2) avec du citrate de plomb en tant que catalyseur balistique, dans sa composition, à un taux massique de 1 % (exemple B1) et de 3,5 % (exemple B2).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).
Deux exemples comparatifs sont aussi présentés avec des propergols similaires à celui de l'exemple 2 selon l'invention mais comprenant, en tant que catalyseur balistique, du sous salicylate de bismuth (C1) et du carbonate de bismuth (C2), en lieu et place du citrate de bismuth.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 (C1) and bismuth carbonate (C2), in place of bismuth citrate.
Les compositions de ces propergols (plus précisément celle de leur pâte avant réticulation) sont présentées dans le tableau 1 ci-après.The compositions of these propellants (more precisely that of their pulp before crosslinking) are presented in Table 1 below.
Les mêmes produits ont évidemment été utilisés pour tous les exemples. Pour ce qui concerne les charges de RDX, elles étaient constituées à 68 % en masse d'un RDX d'une classe granulométrique 0 - 100 µm et à 32 % en masse d'un RDX d'une classe granulométrique 2,5 - 5 µm.
On a donc préparé des produits pyrotechniques composites (propergols) présentant les compositions massiques données dans le tableau 1 ci-dessus. A cette fin, le procédé précisé ci-dessous (voir le paragraphe ci-après intitulé « préparation ») a été mis en oeuvre.Thus, composite pyrotechnic products (propellants) having the mass compositions given in Table 1 above were prepared. For this purpose, the process specified below (see the paragraph below entitled "preparation") has been implemented.
On s'est intéressé à la vie de pot des pâtes de propergol (intermédiaires) préparées. Ladite vie de pot a été déterminée en mettant en oeuvre les mesures de viscosité comme indiqué ci-dessous (voir le paragraphe ci-après intitulé « détermination de la vie de pot »). Les résultats figurent dans la première partie du tableau 2 ci-après.There was interest in the pot life of propellant pastes (middlings) prepared. Said pot life was determined by carrying out the viscosity measurements as indicated below (see the paragraph below titled "determining the pot life"). The results appear in the first part of Table 2 below.
Ledit Tableau 2 renferme également, dans sa seconde partie, des résultats de vitesse de combustion mesurées à différentes pressions, sur les propergols finalement obtenus.Said Table 2 also contains, in its second part, combustion rate results measured at different pressures, on the finally obtained propellants.
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 40°C.In a kneader, the (glycidyl polyazide precursor polymer) was introduced, followed by plasticizers (BTTN / TMETN) and stabilizers (MNA / 2-NDPA) of said plasticizers. The mixture was kneaded for 15 minutes at a temperature of 40 ° C.
On a ensuite ajouté audit mélange, sous agitation, les charges énergétiques organiques (RDX), par portion, puis les additifs (autres que les agent et catalyseur de réticulation (Desmodur® N 3300 et DBTL)) et le catalyseur de combustion. L'agitation a alors été poursuivie pendant 2 h 30, toujours à la température de 40°C et sous un vide de 10 mm de Hg (qui a permis le dégazage du milieu), pour l'obtention d'une pâte homogène.The organic energy charges (RDX), per portion, were then added to the mixture while stirring, followed by the additives (other than the crosslinking agent and catalyst (Desmodur® N 3300 and DBTL)) and the combustion catalyst. Stirring was then continued for 2 h 30, still at the temperature of 40 ° C and under a vacuum of 10 mm Hg (which allowed the degassing of the medium), to obtain a homogeneous paste.
Le catalyseur de réticulation (DBTL (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. Ledit agent de réticulation (Desmodur® N 3300) a enfin été ajouté et le milieu a encore été agité 15 min (toujours à 40°C et sous vide).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 stirred for 15 minutes (still at 40 ° C. and under vacuum).
On a ainsi préparé des lots de 2 kg de pâte de propergol.Thus, batches of 2 kg of propellant paste were prepared.
On a prélevé un échantillon de chacune des pâtes de propergol ainsi préparées pour la détermination de la vie de pot.A sample of each of the propellant pastes thus prepared was taken for pot life determination.
Le reste de chacune des pâtes de propergol préparées a alors été coulé dans une structure adaptée puis soumis au traitement thermique ci-après : cuisson pendant 75 heures à une température de 50°C.The remainder of 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.
La vie de pot 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 40°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 15 h.
On propose les commentaires ci-après au sujet des résultats du tableau 2.The following comments on the results in Table 2 are proposed.
Comme attendu, les pâtes des propergols de référence, sans catalyseur balistique (exemple A) ou contenant du citrate de plomb comme catalyseur balistique (exemples B1 et B2) ont atteint la valeur (de viscosité) de 15 kPo au-delà de 24 h, répondant donc au critère de coulabilité industrielle.As expected, 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.
La pâte de propergol de l'exemple 1 (selon l'invention) incorporant du citrate de bismuth à un taux massique de 1% a présenté des propriétés de coulabilité équivalentes à celles des propergols de référence A (sans catalyseur balistique) et B1 (renfermant 1% massique de citrate de Pb).The propellant paste of Example 1 (according to the invention) incorporating bismuth citrate at a mass content of 1% had flowability properties equivalent to those of the reference propellants A (without ballistic catalyst) and B1 (containing 1% by weight of Pb citrate).
L'exemple 2 (selon l'invention) montre que, même à un taux massique élevé (4 %) de citrate de bismuth, la pâte de propergol a conservé une viscosité inférieure ou égale à 15 kPo au moins pendant 16 h, ce qui est au-delà du temps minimal de 15 h (requis pour assurer industriellement les opérations de coulée de la pâte).Example 2 (according to the invention) 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).
La viscosité des pâtes des propergols des exemples comparatifs C1 et C2 a dépassé la valeur maximale de viscosité acceptable (15 kPo) en moins d'une heure (ce qui est bien en deçà des 15 h requises). Ceci démontre la sélection particulièrement pertinente du couple PAG/citrate de bismuth, selon l'invention.The viscosity of the propellant pastes of Comparative Examples C1 and C2 exceeded the maximum acceptable viscosity value (15 kPo) in less than one hour (which is well below the required 15 hours). This demonstrates the particularly relevant selection of the pair PAG / bismuth citrate, according to the invention.
Le tableau 2 montre aussi que le catalyseur balistique (catalyseur de combustion), citrate de bismuth, confère aux propergols selon l'invention des vitesses de combustion, en fonction de la pression, très supérieures à celles du propergol A de référence (sans catalyseur balistique dans sa composition), et proches de celles des propergols B1 et B2 comprenant, dans leur composition, du citrate de plomb (produit toxique) en tant que catalyseur de combustion.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.
Claims (9)
- A composite pyrotechnic product containing organic energetic charges and a combustion catalyst in a plasticized binder comprising a cured energetic polymer and at least one energetic plasticizer, the product being characterized in that:• said cured energetic polymer consists of a glycidyl azide polymer (GAP) having a number average molecular weight (Mn) lying in the range 700 g/mol to 3000 g/mol, cured via its hydroxyl terminal functions with at least one curing agent of polyisocyanate type; and• said combustion catalyst consists of bismuth citrate.
- The composite pyrotechnic product according to claim 1, characterized in that said glycidyl azide polymer (GAP) has a number average molecular weight (Mn) lying in the range 1700 g/mol to 2300 g/mol.
- The composite pyrotechnic product according to claim 1 or claim 2, characterized in that said at least one energetic plasticizer is of the nitrate and/or nitramine type.
- The composite pyrotechnic product according to any one of claims 1 to 3, characterized in that said organic energetic charges are selected from: hexogen, octogen, hexanitrohexaazaisowurtzitane, nitroguanidine, ethylene dinitramine, N-guanylurea dinitramide, 1,1-diamino-2,2-dinitro ethylene, bis(triaminoguanidinium)-5,5'-azotetrazolate, dihydrazinium 5,5'-azotetrazolate, 5,5'-bis(tetrazolyl)hydrazine, bis(2,2-dinitropropyl) nitramine, and nitropyrazole charges, and mixtures of such charges.
- The composite pyrotechnic product according to any one of claims 1 to 4, characterized in that it contains 1% to 6% by weight, advantageously 3% to 5% by weight, of said bismuth citrate.
- The composite pyrotechnic product according to any one of claims 1 to 5, characterized in that it further contains at least one additive.
- The composite pyrotechnic product according to claim 6, characterized in that said at least one additive comprises at least one curing catalyst and/or at least one stabilizer agent for said at least one energetic plasticizer.
- The composite pyrotechnic product according to any one of claims 1 to 7, characterized in that its composition contains the following, expressed in percentages by weight:• 50% to 70%, advantageously 55% to 65%, of said organic energetic charges;• 10% to 14% of said cured energetic polymer;• 10% to 30%, advantageously 15% to 25%, of said at least one energetic plasticizer;• 1% to 6%, advantageously 3% to 5%, of said bismuth citrate; and• 0 to 4%, advantageously 0.1% to 4%, of at least one additive.
- A method of preparing a composite pyrotechnic product according to any one of claims 1 to 8, characterized in that it comprises:• preparing a homogeneous paste by:a) incorporating, at a temperature lying in the range 35°C to 55°C, in said glycidyl azide polymer, said at least one energetic plasticizer, organic energetic charges, and other ingredients constituting said desired composite pyrotechnic product with the exception of any curing agent and any curing catalyst; andb) stirring the resulting mixture under a partial vacuum at a temperature lying in the range 35°C to 55°C;• under a partial vacuum, at a temperature lying in the range 35°C to 55°C, incorporating in said resulting homogeneous paste, said at least one curing agent and optionally at least one curing catalyst, followed by stirring the resulting mixture;• casting said stirred resulting mixture in at least one structure; and• heat treating said cast stirred resulting mixture in said at least one structure.
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PCT/FR2015/052888 WO2016066945A1 (en) | 2014-10-28 | 2015-10-27 | Efficient composite pyrotechnic product with no pb in the composition thereof and preparation of same |
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EP15808698.3A Active EP3212594B1 (en) | 2014-10-28 | 2015-10-27 | Efficient composite pyrotechnic product with no lead in the composition thereof and preparation of same |
Country Status (8)
Country | Link |
---|---|
US (1) | US20180290945A1 (en) |
EP (1) | EP3212594B1 (en) |
JP (1) | JP6510640B2 (en) |
KR (1) | KR102621576B1 (en) |
FR (1) | FR3027597B1 (en) |
IL (1) | IL251766B (en) |
PL (1) | PL3212594T3 (en) |
WO (1) | WO2016066945A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3056583B1 (en) * | 2016-09-26 | 2018-10-19 | Airbus Safran Launchers Sas | COMPOSITE PYROTECHNIC PRODUCT COMPRISING A POTASSIUM SALT-TYPE ANTI-LIGHT AGENT |
FR3090629B1 (en) * | 2018-12-20 | 2021-07-23 | Arianegroup Sas | Process for the preparation of composite pyrotechnics |
FR3096680B1 (en) | 2019-06-03 | 2021-09-24 | Arianegroup Sas | composite pyrotechnic product |
CN112500253B (en) * | 2020-12-02 | 2022-04-12 | 湖北航天化学技术研究所 | Temperature-sensitive time-varying high-energy solid propellant |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4268450A (en) * | 1977-08-08 | 1981-05-19 | Rockwell International Corporation | Energetic hydroxy-terminated azido polymer |
JPS63248791A (en) * | 1987-04-06 | 1988-10-17 | 日本油脂株式会社 | High energy binder type composite solid propellant |
FR2648809B1 (en) * | 1989-06-21 | 1991-09-13 | Livbag Snc | SOLID GAS GENERATOR COMPOSITION AND ITS USE IN GAS GENERATORS FOR AIR BAGS FOR PROTECTING PASSENGERS OF A MOTOR VEHICLE |
JPH075425B2 (en) * | 1989-10-06 | 1995-01-25 | 防衛庁技術研究本部長 | Gas generating composition |
JPH07165483A (en) * | 1993-12-13 | 1995-06-27 | Daicel Chem Ind Ltd | Gas generating composition |
FR2727401B1 (en) * | 1994-11-29 | 1996-12-27 | Poudres & Explosifs Ste Nale | COMPOSITIONS MODIFYING BALLISTIC PROPERTIES AND PROPERGOLS CONTAINING SUCH 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 (en) | 2000-06-27 | 2009-04-07 | The Minister Of National Defence | Insensitive melt cast explosive compositions containing energetic thermoplastic elastomers |
EP1186582A1 (en) * | 2000-09-08 | 2002-03-13 | Her Majesty in Right of Canada, as represented by the Minister of National Defence | Insensitive propellant formulations containing energetic copolyurethane thermoplastic elastomers |
DE202004009449U1 (en) * | 2004-06-15 | 2004-10-28 | Trw Airbag Systems Gmbh | Gas generating composition |
US8172965B2 (en) * | 2009-10-14 | 2012-05-08 | Raytheon Company | Explosive compositions and methods for fabricating explosive compositions |
DE102010020776B4 (en) * | 2010-05-18 | 2015-03-05 | Diehl Bgt Defence Gmbh & Co. Kg | Propellant charge and method for its production |
GB2512346B (en) * | 2013-03-27 | 2021-06-30 | Bae Systems Plc | Non-phthalate propellants |
-
2014
- 2014-10-28 FR FR1402431A patent/FR3027597B1/en active Active
-
2015
- 2015-10-27 EP EP15808698.3A patent/EP3212594B1/en active Active
- 2015-10-27 WO PCT/FR2015/052888 patent/WO2016066945A1/en active Application Filing
- 2015-10-27 KR KR1020177014380A patent/KR102621576B1/en active IP Right Grant
- 2015-10-27 JP JP2017522927A patent/JP6510640B2/en active Active
- 2015-10-27 PL PL15808698T patent/PL3212594T3/en unknown
- 2015-10-27 US US15/522,608 patent/US20180290945A1/en not_active Abandoned
-
2017
- 2017-04-18 IL IL251766A patent/IL251766B/en active IP Right Grant
Non-Patent Citations (1)
Title |
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None * |
Also Published As
Publication number | Publication date |
---|---|
EP3212594A1 (en) | 2017-09-06 |
WO2016066945A1 (en) | 2016-05-06 |
KR20170101897A (en) | 2017-09-06 |
IL251766B (en) | 2020-04-30 |
FR3027597A1 (en) | 2016-04-29 |
FR3027597B1 (en) | 2016-12-09 |
US20180290945A1 (en) | 2018-10-11 |
JP6510640B2 (en) | 2019-05-08 |
PL3212594T3 (en) | 2019-01-31 |
JP2017538648A (en) | 2017-12-28 |
IL251766A0 (en) | 2017-06-29 |
KR102621576B1 (en) | 2024-01-05 |
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