EP3071536A1 - Produit pyrotechnique composite a liant réticule et son procédé de préparation - Google Patents
Produit pyrotechnique composite a liant réticule et son procédé de préparationInfo
- Publication number
- EP3071536A1 EP3071536A1 EP14814912.3A EP14814912A EP3071536A1 EP 3071536 A1 EP3071536 A1 EP 3071536A1 EP 14814912 A EP14814912 A EP 14814912A EP 3071536 A1 EP3071536 A1 EP 3071536A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- charges
- crosslinking
- mol
- polyurethane
- composite
- 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
- 239000011230 binding agent Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 52
- 238000004132 cross linking Methods 0.000 claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 36
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 26
- 229920000728 polyester Polymers 0.000 claims abstract description 14
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 13
- 239000003380 propellant Substances 0.000 claims abstract description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 11
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims abstract description 9
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 72
- QCOXCILKVHKOGO-UHFFFAOYSA-N n-(2-nitramidoethyl)nitramide Chemical compound [O-][N+](=O)NCCN[N+]([O-])=O QCOXCILKVHKOGO-UHFFFAOYSA-N 0.000 claims description 21
- 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 16
- 235000011837 pasties Nutrition 0.000 claims description 14
- 239000012467 final product Substances 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 7
- 239000004615 ingredient Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 238000003490 calendering Methods 0.000 claims description 6
- 239000000028 HMX Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 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 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- -1 2,2 -dinitropropyl Chemical group 0.000 claims description 4
- MNANQFINLWEMEJ-UHFFFAOYSA-N bis(prop-2-ynyl) butanedioate Chemical compound C#CCOC(=O)CCC(=O)OCC#C MNANQFINLWEMEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 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
- MZRUFMBFIKGOAL-UHFFFAOYSA-N 5-nitro-1h-pyrazole Chemical compound [O-][N+](=O)C1=CC=NN1 MZRUFMBFIKGOAL-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 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 2
- FXYYVODGZXUHLT-UHFFFAOYSA-N 2h-tetrazol-5-ylhydrazine Chemical compound NNC=1N=NNN=1 FXYYVODGZXUHLT-UHFFFAOYSA-N 0.000 claims description 2
- BSPUVYFGURDFHE-UHFFFAOYSA-N Nitramine Natural products CC1C(O)CCC2CCCNC12 BSPUVYFGURDFHE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- UDTFMMZGEOHGNU-WAYWQWQTSA-N bis(prop-2-ynyl) (z)-but-2-enedioate Chemical compound C#CCOC(=O)\C=C/C(=O)OCC#C UDTFMMZGEOHGNU-WAYWQWQTSA-N 0.000 claims description 2
- YFIBSNDOVCWPBL-UHFFFAOYSA-N hexa-1,5-diyne Chemical group C#CCCC#C YFIBSNDOVCWPBL-UHFFFAOYSA-N 0.000 claims description 2
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- SQSPRWMERUQXNE-UHFFFAOYSA-N Guanylurea Chemical compound NC(=N)NC(N)=O SQSPRWMERUQXNE-UHFFFAOYSA-N 0.000 claims 1
- 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
- 125000000524 functional group Chemical group 0.000 claims 1
- MJVUDZGNBKFOBF-UHFFFAOYSA-N n-nitronitramide Chemical compound [O-][N+](=O)N[N+]([O-])=O MJVUDZGNBKFOBF-UHFFFAOYSA-N 0.000 claims 1
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 19
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 238000007493 shaping process Methods 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 229920001187 thermosetting polymer Polymers 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- 239000004416 thermosoftening plastic Substances 0.000 description 5
- 239000000020 Nitrocellulose Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 229920001220 nitrocellulos Polymers 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001345 alkine derivatives Chemical class 0.000 description 3
- 230000000295 complement effect Effects 0.000 description 3
- 229920006037 cross link polymer Polymers 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000002360 explosive Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000003852 triazoles Chemical class 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000006736 Huisgen cycloaddition reaction Methods 0.000 description 2
- 150000001540 azides Chemical class 0.000 description 2
- 239000004204 candelilla wax Substances 0.000 description 2
- 229940073532 candelilla wax Drugs 0.000 description 2
- 235000013868 candelilla wax Nutrition 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000003628 erosive effect Effects 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
- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000000802 nitrating effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- CCCDQXBAOOBBHP-UHFFFAOYSA-N NC(=O)N.[N+](=O)([O-])C=C[N+](=O)[O-] Chemical compound NC(=O)N.[N+](=O)([O-])C=C[N+](=O)[O-] CCCDQXBAOOBBHP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 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 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229960003711 glyceryl trinitrate Drugs 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 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
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0008—Compounding the ingredient
- C06B21/0025—Compounding the ingredient the ingredient being a polymer bonded explosive or thermic component
Definitions
- the present invention relates to composite pyrotechnic products, particularly suitable as propellant powders for tube weapons (more particularly for tank artillery). These are composite pyrotechnic products, which contain a high level of energy charges in an energy crosslinked binder. These products are particularly interesting, especially in terms of strength (of energy power), vulnerability (see below a reminder on this concept, familiar to the skilled person), and scope of application as to the nature of loads that they can contain. They can opportunely be optimized in terms of erosivity.
- the present invention also relates to a process for preparing said composite pyrotechnic products. Said method is particularly easy to implement. It requires no solvent or precipitation for the implementation of shaping while the crosslinking begins, or pre-crosslinking step.
- Known propellant powders consisting of one or more gelatinized energy bases having a homogeneous appearance (hence their name).
- homogeneous propellant powders mention may be made of "smoke-free" powders based on nitrocellulose alone or based on a nitrocellulose-nitroglycerine mixture.
- organic (powdery) energy charges In order to improve the energy performance of these "homogeneous" powders, it has been sought to incorporate organic (powdery) energy charges. These charged powders no longer have a homogeneous appearance, but a heterogeneous appearance in which we distinguish on the one hand, the energy binder and on the other hand, the charges.
- Such charged powders are said “Composite” or “heterogeneous”. Such charged powders are for example described in the French patent application FR 2,488,246.
- Vulnerability is defined as the property that powders can be able to ignite and deflag under the effect of a physical, random, undesired phenomenon, such as the impact of a projectile. Vulnerability is a major defect for powders intended to be loaded on board battle tanks. The development of modern combat gear has therefore led the skilled person to look for propellant powders that are not very vulnerable.
- inert binder composite powders consisting mainly of organic energy charges in a synthetic resin.
- Such powders are much less vulnerable than homogeneous powders or composites with energy binders (nitrocellulose).
- energy binders nitrocellulose.
- these powders must, in order to deliver the necessary energy during firing, contain very high levels of charges, often close to 80% of the total mass of the powder.
- the inert binder composite powders thus have the characteristic of containing very little binder with respect to their powdery filler.
- Inert binders of synthetic origin which can be used in the preparation of composite pyrotechnic products and present in their composition, exist as thermoplastic binders and as heat-curable binders (obtained from oligomers).
- thermoplastic binders allow, in theory, temperature, a mechanical work of the product to give it the desired geometry. It should, however, of course, that the working temperature (to which the binder is deformable) is compatible with the stability of the present charges and, with reference to this unavoidable requirement, it is often necessary to involve a solvent. The intervention of such a solvent increases the implementation of the process.
- Patent Application EP 0 036 481 describes a process for manufacturing composite explosives with a thermoplastic binder.
- the patent application IN 498 / DEL / 2001 discloses a method of preparing propellant containing hexogen (RDX) fillers in a thermoplastic binder.
- RDX hexogen
- thermosetting binders obtained from oligomers
- polyurethane binders crosslinkable
- thermosetting binders
- thermosetting binders To operate without solvent, with thermosetting binders, said skilled in the art has made extensive use of the so-called “casting” or “global” technique, which consists in simultaneously mixing in a kneader the liquid elemental constituents of the resin and the energy charges and to cast, before polymerization, the mixture thus obtained in a mold to conduct the polymerization itself.
- This technique which has been widely described, for example in the French patent applications FR 2 109 102, FR 2 196 998, FR 2 478 623 and FR 2 491 455, may be suitable for the manufacture of composite solid propellants for rocket engines or rockets, or the manufacture of composite explosives for gear heads, which are most often used in the form of large diameter products, but is totally unsuitable for the industrial manufacture of composite powders large, medium and small calibres and more generally to that of certain composite pyrotechnic products;
- the first which consists in mixing in a kneader the constituents of the resin with the energetic charges, to initiate the crosslinking of the resin and, during crosslinking, to perform, in a very short time, the shaping of the product, as described for example in the French patent applications FR 1 409 203 and FR 2 159 826.
- This technique requires a sharp adjustment of the kinetics of crosslinking to allow the dough to work and because of this, it is difficult to manage at industrial scale;
- the composite pyrotechnic products obtained by this second technique mainly consist, on the one hand, of a polymeric binder (for example polyurethane) obtained by reaction of a polyhydroxylated prepolymer (having a number-average molecular weight of between 2000 and 5000 and an average functionality of hydroxyl groups (OH greater than 2 and less than 3) (PBHT, polyether) , polyester, for example) with a crosslinking agent (diisocyanate), and secondly, by an energetic charge, preferably octogen (HMX) or hexogen (RDX), at a rate of about 80% by weight.
- a polymeric binder for example polyurethane
- a first step mixing said polyhydroxy prepolymer with said energetic charge and with a quantity of diisocyanate of between 50% and 90% by weight of the stoichiometric amount necessary for the complete polymerization (reaction) of all the hydroxyl groups (OH) of said prepolymer and for carrying out the condensation reaction of the isocyanate groups (NCO) on the hydroxyl groups (OH) so as to obtain a partially polymerized (crosslinked) paste; + in a second step, mixing with said partially polymerized (crosslinked) pulp thus obtained the complement of diisocyanate necessary to reach said stoichiometric amount necessary for complete polymerization (crosslinking) and extruding the pasty mixture thus obtained; then,
- the technique in question thus comprises two polymerization or crosslinking steps, more specifically a first pre-crosslinking step (or first crosslinking step) with an amount of isocyanate allowing a partially polymerized (crosslinked) paste to be obtained, exhibiting adequate mechanical strength and cohesion for the implementation of the continuation of the process (in particular extrusion) and a second crosslinking step leading to the final product with the desired crosslinked binder.
- first pre-crosslinking step or first crosslinking step
- isocyanate allowing a partially polymerized (crosslinked) paste to be obtained, exhibiting adequate mechanical strength and cohesion for the implementation of the continuation of the process (in particular extrusion)
- second crosslinking step leading to the final product with the desired crosslinked binder.
- the dosages of the crosslinking agent (diisocyanate) for the implementation of the pre-crosslinking are delicate. They require great precision.
- the field of application of said technique is limited, in view of the nature of the intervening crosslinking agent (of isocyanate type, to react with hydroxyl functions), as to the nature of the energy charges present, in the extent where certain charges energy (having intrinsic acidity) are likely to react, in a parasitic reaction, with said crosslinking agent (isocyanate type) present.
- the presence of such fillers (EDNA, nitropyrazoles, for example) is therefore problematic for managing the steps of pre-crosslinking and complementary crosslinking.
- the inventors propose new composite pyrotechnic products, particularly suitable as propellant powders for tube weapons, containing a high level of charges in a crosslinked energetic binder.
- Said new composite pyrotechnic products are optimized in terms of strength (they contain a high energy charge rate in an energy binder), vulnerability (they do not contain nitrocellulose and can advantageously contain energy charges that are not very vulnerable), process obtaining (said method is easy to implement: without solvent, without precipitation for the implementation of a shaping while the crosslinking begins, without pre-crosslinking) and they can also be optimized in terms of erosivity ( they can advantageously contain EDNA charges as a total or partial substitution of RDX charges).
- the present invention thus relates to new composite pyrotechnic products. They are of the crosslinked binder type containing organic energy charges (see above). Characteristically, their compositions, expressed in percentages by weight, contain:
- a crosslinked energetic binder obtained by crosslinking, via only 8 to 12% of its azide functions, of a glycidyl polyazide (PAG) having a number-average molecular weight (Mn) of between 700 and 3000 g / mol, with at least one crosslinking agent containing at least two propargyl functions in its chemical formula, in the presence of a polymeric gum, chosen from polyurethane-polyester gums, polyurethane-polyether gums and mixtures thereof, of which the number average molecular weight is greater than 20,000 g / mol and the Mooney viscosity is between 20 and 70 ML (5 + 4) at 100 ° C; said polymeric gum representing from 1 to 5% by weight of the composition of said pyrotechnic product.
- PAG glycidyl polyazide
- the composite pyrotechnic products of the invention therefore contain a high level of organic energy charges: from 78 to 90% by weight, advantageously from 80 to 86% by weight.
- organic loads the mineral charges having been discarded insofar as they generate solid particles
- organic energy charges known per se and, for the most part, already conditioned according to the prior art in an organic polymeric binder. conventional (such as PBHT), in particular crosslinked.
- RDX hexogen
- HMX octogen
- NGU nitroguanidine
- EDNA ethylene dinitramine
- GUDN N-guanylurea dinitramide
- 1,1-diamino-2, 2-dinitroethylene FOX 7 (DADE)
- TAGZT 5,5'-azotetrazolate bis (5-azotetrazolate)
- DHDZT dihydrazinium 5,5'-azotetrazolate
- HBT bis (2,2-dinitropropyl) nitramine
- BDNPN 2,2-dinitropropyl) nitramine
- organic energetic charges of EDNA particularly preferably, there is a mixture of EDNA charges and RDX charges. It is by no means excluded to find only RDX loads or EDNA loads, but as noted above, mixes of EDNA loads and RDX loads can achieve an optimum in reference to the strength tradeoff. / erosivity. It is understood that the more these mixtures contain RDX, the more they are energetic but the more they are erosive.
- the energy charges are in the form of solid grains, distributed homogeneously within the crosslinked binder. These solid grains suitably have, in a known manner per se, several particle size distributions.
- the binder It is present in a proportion of 10 to 22% by weight; these 10 to 22% by weight including 1 to 5% of gum. It is a thermoset binder (crosslinked) in the presence of a gum, obtained from a thermosetting polymer (crosslinkable) in the presence of a gum. It is such a binder, energetic, obtained from such a polymer, energetic.
- one polymer must read “at least one polymer” throughout the present text. Indeed, it is not excluded from the scope of the invention that a mixture of at least two polymers (each of the type indicated and having different molecular weights and / or branching ratios) is used.
- the energy polymer in question is a glycidyl polyazide (PAG).
- Mn number-average molecular weight
- Said polymer is a polyazide, hence 1) its energetic properties and 2) its ability to be crosslinked with crosslinking agents other than isocyanates.
- crosslinking only involves 8 to 12% of its azide functions (such a low level of crosslinking, used on the polymer having the above molecular weight, makes it possible to obtain the final product with suitable mechanical properties) .
- Said crosslinked polymer thus retains its energetic properties.
- the binder of the composite pyrotechnic products of the invention is therefore, as indicated below. above, an energy binder.
- the force of said composite pyrotechnic products of the invention is better understood (containing a high level of energetic charges in an energy (crosslinked) binder).
- the crosslinked binder of the invention is thus obtained by crosslinking a prepolymer, as specified above, with at least one crosslinking agent containing alkyne functions, i.e. via triazole patellae of formula:
- the at least one crosslinking agent used is a compound containing at least two propargyl functions in its chemical formula ("a polypropargyl"), it generally consists of a di- and / or tri-propargyl.
- a polypropargyl generally consists of a di- and / or tri-propargyl.
- it consists of dipropargyl succinate (DPS), dipropargyl maleate (DPM), tripropargyl tricarbylate (TCATP), benzene tripropargyl ester (BETP), and poly (ethylene glycol).
- DPS dipropargyl succinate
- DPM dipropargyl maleate
- TCATP tripropargyl tricarbylate
- BETP benzene tripropargyl ester
- poly (ethylene glycol) poly (ethylene glycol).
- PEG dipropargyl having a number average molecular weight of from 200 to 1500 g / mol.
- DPS dipropargyl succ
- composition of the composite pyrotechnic products of the invention also contains a polymeric gum ("raw rubber") of the type specified.
- Said eraser :
- polyurethane-polyester gums i.e. of polyurethane nature with polyester-type flexible segments
- polyurethane-polyether gums i.e. of polyurethane-type polyurethane-type nature
- Such a rubber is perfectly suitable for the purposes of the invention, insofar as it allows shaping of the mixture to be crosslinked at a temperature below 100 ° C. (which is entirely compatible with the present charges), and this, without any use of solvent, without precipitation (for the implementation of said shaping while the crosslinking begins) and without any pre-crosslinking.
- Said gum is miscible with the polymer (PAG) (the gum / polymer mixture is "stable", no exudation phenomenon is observed). It performs its (beneficial) action by being present in small quantities (it represents at most 5% of the total mass of the product): its presence is not too detrimental in reference to the strength of said products.
- Said gum generally consists of a polyurethane-polyester gum or a polyurethane-polyether, but mixtures of at least two gums (at least two polyurethane-polyester gums, at least two polyurethane-polyether gums or at least one polyurethane-polyester gum and at least one polyurethane-polyether gum, such gum mixtures (gums within the meaning of the invention) constituting a gum within the meaning of the invention) having the required properties (mentioned above) may be used.
- Said gum advantageously consists of a polyurethane-polyester gum.
- This gum therefore intervenes upstream of the crosslinking process, upstream of the forming step, as a manufacturing aid. It is this which makes it possible to confer, without danger, on the polymer charged, due to its properties (sufficient molecular mass and adequate viscosity), the mechanical and cohesion required. It is this which allows the easy preparation, without solvent, without precipitation (for the implementation of a shaping while the reticulation begins) and without pre-crosslinking, composite pyrotechnic products of the invention. It acts at suitable temperatures (below 100 ° C) as a thickener and cohesive agent of said charged polymer. Said gum, auxiliary manufacturing, intervening upstream of any crosslinking, makes it possible, easy, the manufacture of composite pyrotechnic products of the invention. In the end, it is entangled in the cross-linked polymer network (PAG).
- PAG cross-linked polymer network
- the crosslinked binder is therefore the product resulting from the reaction, between the polymer (PAG) and the at least one crosslinking agent, implemented in the presence of the gum and that it therefore contains , in addition to said crosslinked polymer via triazole patches, said gum.
- composition of the composite pyrotechnic products of the invention is therefore essentially composed of energy charges and crosslinked binder (containing said gum). It may consist of 100% by mass of said energy charges and said crosslinked binder (containing said gum). It is generally at least 95% by weight, more generally at least 98% by weight. It can not be excluded that it contains in addition at least one other additive; said gum, present in small quantities, which can rightly be considered as an additive: it is not an essential constituent of the binder, it is a manufacturing aid whose intervention allows a simple obtaining of the desired product (according to the method described further in the present text). Such at least one other additive, when present, is generally at a level of 0.1 to 5% by weight, more generally at 0.1 to 2% by weight. It may especially be at least one other additive, chosen from the agents of implementation (candelilla wax and / or paraffin), the plasticizers (energetic or not) and the stabilizers.
- the composite pyrotechnic products of the invention are perfectly suitable as propellant powder for tube weapons. Said composite pyrotechnic products of the invention therefore advantageously consist of such powders.
- the composite pyrotechnic products of the invention, as described above, are also suitable, in particular, as tactical propellant, explosive composition and gas generator.
- Said method constitutes the second object of the present invention. He understands :
- glycidyl polyazide having a number-average molecular mass (Mn) of between 700 and 3,000 g / mol
- a polymeric gum chosen from polyurethane-polyester gums, polyurethane-polyether gums and mixtures thereof, the number-average molecular mass of which is greater than 20,000 g / mol and the Mooney viscosity of which is between 20 and 60 ml. + 4) at 100 ° C; b) obtaining a pasty mixture from said ingredients; the organic energy charges, glycidyl polyazide, polymeric gum being used in adequate proportions with reference to the desired composition of the final product, and said at least one crosslinking agent in the amount necessary for the crosslinking of 8 to 12% of the azide functions said glycidyl polyazide;
- Said method therefore comprises the provision of the constituent (essential) ingredients of the desired composite pyrotechnic products: the fillers + the elements from which the crosslinked binder is obtained, i.e. the polymer, the at least one crosslinking agent and the gum. It has been indicated that the fillers represent between 78 and 90% of the mass of the desired product while the crosslinked binder represents between 10 and 22%, said 10 to 22% including the 1 to 5% of said gum (the complement of said 1 to 5% corresponding to the product of the reaction of the polymer and the at least one crosslinking agent).
- Said at least one crosslinking agent intervenes in the appropriate amount to cross-link the 8 to 12% of the azide functions of the polymer; it generally occurs at less than 5% by weight (more generally between 0.5% and 4%) of the reaction mixture. It is recalled here incidentally that additives, other than said gum, are likely to occur.
- a pasty mixture is thus produced, the precursor of the final product. (crosslinked) targeted.
- a pasty mixture is advantageously made by twin-screw (extrusion) or bi-cylinder, depending on the amounts to implement. It is generally carried out at a temperature between 15 ° C and 45 ° C. It can therefore be performed at room temperature or at a temperature above room temperature. In any case, the intervention of the rubber provides said pasty mixture, which can be manipulated and shaped.
- At least one element is prepared in the third step of the process of the invention (generally n elements are prepared) to a desired shape (directly that desired for the final product (s). (final) or an "intermediate” form from which is obtained after crosslinking (and generally cutting), said (s) product (s) final (s) to the desired shape).
- Said third step is therefore analyzed as a step of shaping the dough.
- This formatting can include spinning or calendering. At the end of such spinning (implemented in a press pot, having an outlet orifice of greater or lesser diameter), a spun product is obtained. This spun product is generally heat treated for crosslinking and then cut into strands (at the desired length).
- Such strands suitable as propellant powders for tube weapons, generally have a length of 2 to 20 mm, for a diameter of 1 to 20 mm (more generally for a diameter of 2 to 15 mm). However, it is not excluded to cut the spun product (thus non-crosslinked strands) and crosslink said strands.
- the calendered product in the form of a plate (such a plate generally has a thickness of 10 to 20 mm), can be directly cut into platelets or heat treated for crosslinking and then cut into platelets.
- steps b and c of said method may comprise:
- twin-screw or twin cylinder twin-screw or twin cylinder
- the pasty mixture, shaped to the desired shape for the final product or an intermediate form, is then heat-treated.
- the heat treatment must make it possible to ensure the expected result (the crosslinking of the polymer) at a non-excessive temperature (compatible with the presence of energy charges at a high rate). Generally, said temperature is above 45 ° C and remains below 80 ° C.
- the crosslinking is carried out at 55 ° C. (+/- 5 ° C.).
- Said at least one thermally treated element corresponds to the at least one product of the invention sought or enables it to be obtained, generally by cutting.
- Binder PAG, marketed by Eurenco (Mn (number average molecular weight): 1900).
- Gum UREPAN ® 643 G, sold by RheinChemie, (polyaddition product of diphenylmethane diisocyanate and a polyester). It has the following characteristics:
- EDNA ethylene dinitramine
- the medium was stirred for 30 minutes at room temperature.
- the mixture was poured on a bath of cold water at about 5 ° C. with stirring.
- the solid was then separated from the mother liquors by filtration, and washed several times with distilled water to neutral pH and then filtered off. It was then taken up, wet, for the synthesis of EDNA.
- the decarboxylation step was carried out by adding DNEU to an aqueous solution buffered with hot sodium acetate. Gaseous evolution (of CO 2 ) was observed, which necessitated a fractional introduction of the powder.
- the reaction medium was then cooled so that the EDNA precipitated.
- the suspension was then filtered and dried. A yield of 85% was obtained.
- the obtaining of EDNA has been confirmed by infra-red.
- Crosslinking agent propargyl polyethylene glycol with a molecular weight of 1,000 g / mol (dipropargyl PEG 1000)
- PEG-1000 50 g
- 40% by weight sodium hydroxide (6 g) was added and then propargyl bromide, in 80% by weight solution in toluene (13.36 ml, 0.12 mol), with stirring, dropwise at room temperature. drop.
- the medium was brought to 65 ° C. over a period of 36 hours.
- 150 ml of dichloromethane were added to the medium, brought to room temperature.
- the resulting medium was then washed with water until a pH equal to 7 of the washings.
- the organic solution was then dried and the solvent evaporated.
- the recovered product (35 g) was in the form of a wax.
- Step b of the process of the invention the pasty mixtures were obtained with a twin cylinder, in a known Persian manner.
- the gum was first introduced between the rolls of the bi-roll (rolling mill), brought to a temperature of 38 ° C. It has been softened. Then, a mixture + PAG charges (previously made in a container) was added. To the resulting mixture, the candelilla wax (processing agent) and then the crosslinking agent (in a ratio -C ⁇ CH / -N 3 equal to 10) were then successively added.
- Step c of the process of the invention the pasty mixtures obtained were introduced into a press pot heated to 38 ° C to perform a spinning at a pressure of between 180 and 220 bar.
- Step d of the process of the invention the heat treatment of the spun product was carried out at 50 ° C for 5 days. After cutting (crosslinked spun product), strands of powder (diameter: 10 mm, length: 11 mm) were obtained.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
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- Dispersion Chemistry (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL14814912T PL3071536T3 (pl) | 2013-11-22 | 2014-11-21 | Kompozytowy wyrób pirotechniczny z usieciowanym lepiszczem i sposób jego wytwarzania |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1302708A FR3013706B1 (fr) | 2013-11-22 | 2013-11-22 | Produit pyrotechnique composite a liant reticule et son procede de preparation |
PCT/FR2014/000251 WO2015075328A1 (fr) | 2013-11-22 | 2014-11-21 | Produit pyrotechnique composite a liant réticule et son procédé de préparation |
Publications (2)
Publication Number | Publication Date |
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EP3071536A1 true EP3071536A1 (fr) | 2016-09-28 |
EP3071536B1 EP3071536B1 (fr) | 2017-09-20 |
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ID=50473356
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP14814912.3A Active EP3071536B1 (fr) | 2013-11-22 | 2014-11-21 | Produit pyrotechnique composite a liant réticule et son procédé de préparation |
Country Status (6)
Country | Link |
---|---|
US (1) | US20160289134A1 (fr) |
EP (1) | EP3071536B1 (fr) |
CA (1) | CA2930488A1 (fr) |
FR (1) | FR3013706B1 (fr) |
PL (1) | PL3071536T3 (fr) |
WO (1) | WO2015075328A1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN115180994B (zh) * | 2022-07-12 | 2023-06-09 | 西安近代化学研究所 | 一种光-热双固化烯丙基型含能粘合剂及制备方法 |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3151010A (en) * | 1955-02-11 | 1964-09-29 | Phillips Petroleum Co | Method of preparing a solid composite propellant |
US3026672A (en) * | 1959-06-29 | 1962-03-27 | Phillips Petroleum Co | Composite propellant containing burning rate depressant and method of use |
FR1409203A (fr) | 1961-01-10 | 1965-08-27 | Aerojet General Co | Mélanges propulsifs à base de polyuréthanes |
US3577289A (en) * | 1968-02-12 | 1971-05-04 | Jacque C Morrell | Composite high energy solid rocket propellants and process for same |
GB1316692A (en) | 1970-05-04 | 1973-05-09 | North American Rockwell | Monomers polymerisable to form binders for explosive and propellant compositions and polymers and compositions formed therefrom |
FR2109102A5 (en) | 1970-10-01 | 1972-05-26 | France Etat | Resin bound explosive - contg rounded particles of explosive |
FR2159826A5 (en) | 1971-11-12 | 1973-06-22 | Voith Gmbh | Extruding thermosetting resins - eg polyesters with fibrous fillers to give stable profiles |
FR2268770A1 (en) | 1974-04-24 | 1975-11-21 | Commissariat Energie Atomique | Resin coated explosive compsn - prepd by liquid phase prodn of granules which are then compressed and crosslinked by heating |
FR2319602A1 (fr) * | 1975-07-30 | 1977-02-25 | Poudres & Explosifs Ste Nale | Nouvel explosif composite moule thermostable et procede de fabrication |
DE3010052C2 (de) | 1980-03-15 | 1982-09-09 | Friedrich-Ulf 8899 Rettenbach Deisenroth | Verfahren zur Herstellung von kunststoffgebundenen Explosivstoffen |
JPS56160395A (en) | 1980-03-20 | 1981-12-10 | Hercules Inc | Crosslinked propellant |
US4381958A (en) | 1980-08-07 | 1983-05-03 | Hercules Incorporated | Triaminoguanidine nitrate-containing propellants |
JPS609996B2 (ja) | 1980-10-07 | 1985-03-14 | 日本油脂株式会社 | ニトラミン系コンポジツト推進薬組成物 |
US4335231A (en) * | 1981-04-03 | 1982-06-15 | Uniroyal, Inc. | Sulfur curable millable polyurethane gum |
FR2577919B1 (fr) | 1985-02-27 | 1987-02-20 | Poudres & Explosifs Ste Nale | Procede de fabrication sans solvant de produits pyrotechniques composites a liant thermodurcissable et produits ainsi obtenus, notamment poudres propulsives composites |
US4919737A (en) * | 1988-08-05 | 1990-04-24 | Morton Thiokol Inc. | Thermoplastic elastomer-based low vulnerability ammunition gun propellants |
US6103029A (en) * | 1997-06-23 | 2000-08-15 | The United States Of America As Represented By The Secretary Of The Navy | Triazole cross-linked polymers |
DE69905398T2 (de) * | 1998-11-12 | 2003-06-12 | Alliant Techsystems Inc | Herstellung von energetischen thermoplastischen elastomeren die oligomere urethanbindungen enthalten |
US20050267245A1 (en) * | 2003-03-18 | 2005-12-01 | Sandusky Donald A | Alloy blends of polyurethane and rubber |
US6872266B1 (en) * | 2003-05-30 | 2005-03-29 | The United States Of America As Represented By The Secretary Of The Navy | Triazole crosslinked polymers in recyclable energetic compositions and method of preparing the same |
WO2006025615A1 (fr) * | 2004-09-03 | 2006-03-09 | Kuraray Co., Ltd. | Granule multicouche comprenant des formulations de résines copolymères éthylène/alcool vinylique |
US8501390B2 (en) * | 2006-06-27 | 2013-08-06 | Xiper Innovations, Inc. | Laser engravable flexographic printing articles based on millable polyurethanes, and method |
-
2013
- 2013-11-22 FR FR1302708A patent/FR3013706B1/fr active Active
-
2014
- 2014-11-21 PL PL14814912T patent/PL3071536T3/pl unknown
- 2014-11-21 WO PCT/FR2014/000251 patent/WO2015075328A1/fr active Application Filing
- 2014-11-21 CA CA2930488A patent/CA2930488A1/fr not_active Abandoned
- 2014-11-21 EP EP14814912.3A patent/EP3071536B1/fr active Active
- 2014-11-21 US US15/038,226 patent/US20160289134A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
PL3071536T3 (pl) | 2018-02-28 |
US20160289134A1 (en) | 2016-10-06 |
FR3013706B1 (fr) | 2015-12-25 |
CA2930488A1 (fr) | 2015-05-28 |
WO2015075328A1 (fr) | 2015-05-28 |
EP3071536B1 (fr) | 2017-09-20 |
FR3013706A1 (fr) | 2015-05-29 |
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