EP1216977A2 - Hydrocarbon binder containing pyrotechnic gas-generating compositions and method for continuous manufacturing - Google Patents
Hydrocarbon binder containing pyrotechnic gas-generating compositions and method for continuous manufacturing Download PDFInfo
- Publication number
- EP1216977A2 EP1216977A2 EP01403255A EP01403255A EP1216977A2 EP 1216977 A2 EP1216977 A2 EP 1216977A2 EP 01403255 A EP01403255 A EP 01403255A EP 01403255 A EP01403255 A EP 01403255A EP 1216977 A2 EP1216977 A2 EP 1216977A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- gum
- nitrate
- binder
- compartment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 81
- 239000011230 binding agent Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 5
- 229930195733 hydrocarbon Natural products 0.000 title claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000460 chlorine Substances 0.000 claims abstract description 15
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 15
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 11
- 239000004014 plasticizer Substances 0.000 claims abstract description 11
- 229920000728 polyester Polymers 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000000945 filler Substances 0.000 claims abstract description 7
- -1 nitrogenous organic compound Chemical class 0.000 claims abstract description 7
- 229920001225 polyester resin Polymers 0.000 claims abstract description 6
- 239000004645 polyester resin Substances 0.000 claims abstract description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 238000004898 kneading Methods 0.000 claims description 12
- 235000010344 sodium nitrate Nutrition 0.000 claims description 12
- 239000004317 sodium nitrate Substances 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 230000006835 compression Effects 0.000 claims description 10
- 238000007906 compression Methods 0.000 claims description 10
- 239000000080 wetting agent Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000005751 Copper oxide Substances 0.000 claims description 6
- 229910000431 copper oxide Inorganic materials 0.000 claims description 6
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 claims description 6
- 150000002897 organic nitrogen compounds Chemical class 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 4
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 claims description 4
- XWVQUJDBOICHGH-UHFFFAOYSA-N dioctyl nonanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCC XWVQUJDBOICHGH-UHFFFAOYSA-N 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 3
- 150000001282 organosilanes Chemical class 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 3
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 claims description 2
- BAKYASSDAXQKKY-UHFFFAOYSA-N 4-Hydroxy-3-methylbenzaldehyde Chemical compound CC1=CC(C=O)=CC=C1O BAKYASSDAXQKKY-UHFFFAOYSA-N 0.000 claims description 2
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001541 aziridines Chemical class 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 150000001912 cyanamides Chemical class 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- 238000010924 continuous production Methods 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 239000000470 constituent Substances 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 4
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000002516 radical scavenger Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 17
- 238000002485 combustion reaction Methods 0.000 description 16
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 16
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 16
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 15
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 239000004971 Cross linker Substances 0.000 description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000000567 combustion gas Substances 0.000 description 4
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 4
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 150000001540 azides Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 241000731961 Juncaceae Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- PAUHLEIGHAUFAK-UHFFFAOYSA-N 1-isocyanato-1-[(1-isocyanatocyclohexyl)methyl]cyclohexane Chemical compound C1CCCCC1(N=C=O)CC1(N=C=O)CCCCC1 PAUHLEIGHAUFAK-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
- 239000000006 Nitroglycerin Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229960003711 glyceryl trinitrate Drugs 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000007 metacrylic acid group Chemical group 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0033—Shaping the mixture
- C06B21/0075—Shaping the mixture by extrusion
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
- C06B29/22—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate the salt being ammonium perchlorate
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
Definitions
- the present invention relates to the field technique of pyrotechnic gas generation usable in particular in protection systems occupants of a motor vehicle by means of cushions which are inflated by the combustion gases of a pyrotechnic charge. More specifically the invention relates to pyrotechnic compositions generating acceptable temperatures for automotive safety clean, non-toxic gases. The invention relates to also a continuous manufacturing process for such compositions.
- pyrotechnic gas generators For different pyrotechnic needs and in particular to ensure correct inflation of the cushions protection, pyrotechnic gas generators must supply in extremely short time, around thirty milliseconds, clean gases that is to say free of solid particles liable to create hot spots that can damage the wall cushion, and non-toxic i.e. low nitrogen oxides, carbon oxides and chlorinated products.
- a first family relates to compositions based on alkali or alkaline earth azide in the presence of a mineral oxidant such as potassium nitrate or a metal oxide.
- These compositions which may optionally include a binder have major drawbacks. On the one hand they produce during their combustion a lot of dust which must be filtered by relatively large filtration systems, which increases both the weight and the price of the generator.
- azides are very toxic products which also have the possibility of forming lead azides or other heavy metals which are primary explosives. These compositions are therefore difficult to keep in good conditions for several years in a motor vehicle.
- compositions with nitrocellulose and nitroglycerin base are very interesting because they burn very quickly and without producing dust. However, they have the disadvantage of not be completely stable over time, and at high temperature.
- compositions say "composites” basically made up of a organic binder and by an oxidizing mineral filler like in particular a mineral perchlorate. These compositions are a priori very interesting because they present good burning speed and excellent stability to aging.
- compositions have also been proposed constituted by a silicone binder crosslinkable to room temperature, also known as linking “RTV” (Room Temperature Vulcanizable), and potassium perchlorate, the potassium atom playing the role of internal chlorine sensor.
- RTV Room Temperature Vulcanizable
- Such compositions are, for example, described in patents FR-A-2 190 776 and FR-B-2 213 254 or in their US correspondents US-A-3,986,908 and US-A-3,964,256.
- these compositions exhibit the disadvantage of generating gases very rich in oxygen that are not wanted by the manufacturers of automobile industry.
- compositions constituted by a silicone binder and by a mixture of ammonium perchlorate and sodium nitrate.
- Such compositions do not contain a solvent. They are for example described in French patent FR-A-2 728 562 or in its American correspondent US-A-5 610 444. These compositions generate many clean gases, rich in nitrogen and non-toxic but have the drawback of burning at very high temperatures and produce a high solid residue level.
- the methods of manufacturing existing compositions involve the presence of a solvent to adjust the viscosity.
- the use of a solvent has many drawbacks, especially at the industrial level. The solvent must be removed from the composition and this operation risks creating porosities in the pyrotechnic charge.
- the object of the present invention is precisely to propose such compositions and a method allowing to implement them.
- the invention therefore relates to a gas-generating pyrotechnic composition
- a binder an organic nitrogen compound, additives and an oxidizing charge comprising ammonium perchlorate and a chlorine sensor
- said binder being a hydrocarbon binder containing at least two components, one of the components being constituted by a gum, characterized in that, when the gum is a polyester gum, it is associated with a polyester resin and in that, when the gum is an acrylic gum, it is associated with one of its plasticizers.
- a polymer whose molecular mass is greater than 200,000 is called gum.
- the acrylic gums used are also called acrylic rubbers or polyacrylates. These gums can have reactive terminations of the chlorine / carboxyl, chlorine, hydroxyl or epoxy type.
- the polyester gums used are rubbers with ester units and which can have reactive hydroxyl type terminations.
- Resin is a hydrocarbon polymer whose mass molecular is between 100 and 10,000.
- the binder is formed by the association of an acrylic gum and one of its plasticizers.
- the plasticizer for acrylic gum is chosen from the group consisting of dioctyl adipate and dioctyl azelate.
- a crosslinker will generally be associated with the binder.
- the binder is formed by the association of an eraser polyester and polyester resin.
- the composition further comprises an isocyanate crosslinker.
- the weight content of the charges is greater than or equal to 85% of the total weight of the composition.
- the oxidizing charge includes ammonium perchlorate and a chlorine sensor.
- the chlorine sensor is chosen from the group consisting of sodium nitrate, calcium carbonate, lithium carbonate, potassium nitrate, strontium nitrate, barium nitrate, potassium chlorate, potassium perchlorate and copper oxide.
- a preferred chlorine sensor is sodium nitrate.
- the composition also includes a compound organic nitrogen.
- the organic nitrogen compound is chosen in the group consisting of nitroguanidine, the guanidine nitrate, aminoguanidine nitrate, oxamide, dicyandiamide, guanyl direedinitramide and metallic cyanamides.
- the content by weight of this nitrogen compound is between 3 and 15% of the total weight of the composition.
- the composition also comprises a ballistic catalyst chosen from the group consisting of titanium oxide, copper oxide, basic copper nitrate, copper chromite and iron oxide .
- the preferred ballistic catalyst is iron oxide.
- the weight content of the ballistic catalyst is preferably between 0% and 4% of the total weight of the composition. Among other things, it improves the combustion speed.
- the composition further comprises a wetting agent.
- This wetting agent is chosen from the group consisting of organosilanes, titanates and aziridines.
- the preferred organosilanes are the trialkyl silanes in which the functional group is a vinyl, epoxy, amine or metacrylic group.
- the weight content of the wetting agent is preferably between 0.5% and 2% of the total weight of the composition. This component reduces the residual porosity of the product.
- Ballistic catalyst and wetting agent constitute the preferred additives of the compositions according to the invention.
- the organic nitrogen compound and gum are premixed and introduced into the mixing compartment and mixing through the solids feed opening.
- the pressure of the compression compartment is less than 50 ⁇ 10 3 Pa, ie 500 mbar.
- the temperature of the mixing compartment and mixing is between 15 ° C and 75 ° C.
- the pressure in the extrusion head is between 6.10 6 Pa and 15.10 6 Pa, ie between 60 bars and 150 bars.
- the hydrocarbon binder comprises on the one hand a gum and on the other hand a liquid constituent which is either a resin or a plasticizer.
- a pasty binder is therefore obtained.
- this binder has sufficient strength to be extruded in the form of rods. There is therefore no need for a thickening agent or a solvent.
- the rods are then cut into loads and the structure of the binder is definitively frozen by crosslinking in an oven at a temperature between 100 ° C and 150 ° C.
- Figure 1 represents, in the form of partially cut diagram, an installation allowing the implementation of the method according to the invention.
- the twin-screw extruder-mixer 1 comprises an upstream part 2 in which the operations for mixing and kneading the composition are situated, a downstream part 3 in which the degassing operation for the composition takes place and a head for extrusion 4. During operation, a plug of material is formed which separates the downstream part 2 from the upstream part 3.
- the upstream part 2 will be called “mixing and kneading compartment” and the downstream part 3 "compression compartment".
- the gum and the nitrogenous organic compound are premixed.
- the eraser will be an eraser acrylic and the nitrogen compound will be nitrate of guanidine.
- the inert constituents namely the plasticizer and the various additives
- the oxidizing charges and the gum / nitrogenous organic compound mixture are then introduced.
- the various constituents are continuously introduced into the mixing and kneading compartment.
- Solids A are introduced without solvent by means of a hopper.
- the liquids B are introduced without solvent by means of a metering pump 6.
- the liquids B consist of the plasticizer and the wetting agent.
- Solids A are the acrylic gum / guanidine nitrate mixture, the oxidizing charge comprising ammonium perchlorate and the additives other than the wetting agent. Particles of ammonium perchlorate of two different particle sizes are used.
- the particle size is between 10 ⁇ m and 50 ⁇ m. Since ammonium perchlorate produces chlorine derivatives by combustion, it has a chlorine sensor attached to it.
- the preferred chlorine sensor in the context of the invention is sodium nitrate which fixes the chlorine in the form of sodium chloride of submicron size, therefore without risk of damaging the walls of the airbag.
- Sodium nitrate will also be introduced through the feed opening for solids A.
- the ratio between ammonium perchlorate and sodium nitrate is between 1 and 2.
- the rate of oxidizing charges is preferably around 80% of the total weight of the composition, to have a composition fairly balanced in oxygen balance.
- the weight content of the fillers is greater than or equal to 85% of the total weight of the composition. They are therefore compositions with a highly charged binder. The content of the binder and crosslinker composition will advantageously be close to 15%.
- the preferred additives are the wetting agent and the ballistic catalyst.
- the preferred ballistic catalyst is iron oxide.
- the paste formed in the mixing and kneading compartment 2 is then degassed in the compression compartment 3, under a pressure of less than 30.10 3 Pa, or 300 mbar.
- This paste is then extruded, by means of an extrusion head 4, in the form of rods 8.
- the pressure in the extrusion head is preferably close to 100 bars.
- These rods are then cut into loads 9 using a cutting device 10.
- These loads 9 are recovered by a conveyor belt 11 and routed to an oven 12.
- This oven 12 is heated to a temperature between 100 and 150 ° C. Preferably, this oven is heated to 120 ° C.
- the loads remain approximately 3 hours in this oven so as to complete the crosslinking of the constituents of the binder and thus to freeze the structure of the loads 9.
- the loads 9 have the form of hollow cylindrical blocks most often having axial channels.
- the charges thus formed find their preferred application as pyrotechnic charges in gas generators intended to inflate a protective cushion for occupants of a motor vehicle.
- the rate of combustion of these loads, as well as the rate of solid residues produced and the rate of carbon monoxide and nitrogen oxides produced are particularly suitable for the requirements of automobile safety.
- the examples which follow illustrate, without limitation, certain possibilities of implementing the invention.
- the weight content of the fillers is 87.9%
- the weight content of the fillers is 85%.
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Abstract
Description
La présente invention se rapporte au domaine technique de la génération pyrotechnique de gaz utilisables notamment dans les systèmes de protection des occupants d'un véhicule automobile au moyen de coussins qui sont gonflés par les gaz de combustion d'un chargement pyrotechnique. Plus précisément l'invention concerne des compositions pyrotechniques générant à des températures acceptables pour la sécurité automobile des gaz propres et non toxiques. L'invention concerne également un procédé de fabrication en continu de telles compositions.The present invention relates to the field technique of pyrotechnic gas generation usable in particular in protection systems occupants of a motor vehicle by means of cushions which are inflated by the combustion gases of a pyrotechnic charge. More specifically the invention relates to pyrotechnic compositions generating acceptable temperatures for automotive safety clean, non-toxic gases. The invention relates to also a continuous manufacturing process for such compositions.
Pour différents besoins pyrotechniques et notamment pour assurer un gonflement correct des coussins de protection, les générateurs pyrotechniques de gaz doivent fournir en des temps extrêmement courts, de l'ordre de trente millisecondes, des gaz propres c'est-à-dire exempts de particules solides susceptibles de constituer des points chauds pouvant endommager la paroi du coussin, et non toxiques c'est-à-dire à faible teneurs en oxydes d'azote, en oxydes de carbone et en produits chlorés.For different pyrotechnic needs and in particular to ensure correct inflation of the cushions protection, pyrotechnic gas generators must supply in extremely short time, around thirty milliseconds, clean gases that is to say free of solid particles liable to create hot spots that can damage the wall cushion, and non-toxic i.e. low nitrogen oxides, carbon oxides and chlorinated products.
Diverses familles de compositions pyrotechniques
ont été développées dans ce but.
Un première famille concerne les compositions à
base d'azoture alcalin ou alcalino-terreux en présence
d'un oxydant minéral comme le nitrate de potassium ou
d'un oxyde métallique. Ces compositions qui peuvent le
cas échéant comporter un liant présentent des
inconvénients majeurs. D'une part elles produisent lors
de leur combustion beaucoup de poussières qui doivent
être filtrées par des systèmes de filtration
relativement importants, ce qui augmente à la fois le
poids et le prix du générateur. D'autre part les
azotures sont des produits très toxiques qui présentent
de surcroít la possibilité de former des azotures de
plomb ou d'autres métaux lourds qui sont des explosifs
primaires. Ces compositions sont donc difficiles à
conserver dans de bonnes conditions pendant plusieurs
années dans un véhicule automobile.Various families of pyrotechnic compositions have been developed for this purpose.
A first family relates to compositions based on alkali or alkaline earth azide in the presence of a mineral oxidant such as potassium nitrate or a metal oxide. These compositions which may optionally include a binder have major drawbacks. On the one hand they produce during their combustion a lot of dust which must be filtered by relatively large filtration systems, which increases both the weight and the price of the generator. On the other hand azides are very toxic products which also have the possibility of forming lead azides or other heavy metals which are primary explosives. These compositions are therefore difficult to keep in good conditions for several years in a motor vehicle.
Une seconde famille concerne les compositions à base de nitrocellulose et de nitroglycérine. Ces compositions, encore connues sous l'appellation de « poudres à double base », sont très intéressantes car elles brûlent très vite et sans produire de poussière. Mais elles présentent toutefois l'inconvénient de ne pas être totalement stables dans le temps, et à haute température.A second family concerns compositions with nitrocellulose and nitroglycerin base. These compositions, still known as "Double base powders" are very interesting because they burn very quickly and without producing dust. However, they have the disadvantage of not be completely stable over time, and at high temperature.
Une troisième famille concerne les compositions dites « composites » constituées fondamentalement par un liant organique et par une charge minérale oxydante comme notamment un perchlorate minéral. Ces compositions sont à priori très intéressantes car elles présentent une bonne vitesse de combustion et une excellente stabilité au vieillissement.A third family concerns the compositions say "composites" basically made up of a organic binder and by an oxidizing mineral filler like in particular a mineral perchlorate. These compositions are a priori very interesting because they present good burning speed and excellent stability to aging.
Il a ainsi été proposé par le brevet FR-A-2 137 619 ou par son correspondant US-A-3,723,205 des compositions dont le liant est un chlorure de polyvinyle et dont la charge oxydante est un perchlorate d'ammonium en présence de nitrate de sodium comme capteur interne de chlore. Néanmoins l'emploi d'un liant chloré en présence de charges énergétiques est d'une mise en oeuvre délicate, notamment au plan de la sécurité et de la non toxicité des gaz générés.It has thus been proposed by patent FR-A-2 137 619 or by its correspondent US-A-3,723,205 of the compositions whose binder is polyvinyl chloride and whose oxidizing charge is an ammonium perchlorate in presence of sodium nitrate as internal sensor of chlorine. However, the use of a chlorinated binder in the presence of energy charges is an implementation delicate, especially in terms of security and safety toxicity of the gases generated.
Il a aussi été proposé des compositions composites constituées par un liant silicone réticulable à température ambiante, encore connu sous l'appellation de liant « RTV » (Room Temperature Vulcanizable), et de perchlorate de potassium, l'atome de potassium jouant le rôle de capteur interne de chlore. De telles compositions sont, par exemple, décrites dans les brevets FR-A-2 190 776 et FR-B-2 213 254 ou dans leurs correspondants américains US-A-3,986,908 et US-A-3,964,256. Ces compositions présentent cependant l'inconvénient de générer des gaz très riches en oxygène qui ne sont pas recherchés par les constructeurs de l'industrie automobile.Composite compositions have also been proposed constituted by a silicone binder crosslinkable to room temperature, also known as linking “RTV” (Room Temperature Vulcanizable), and potassium perchlorate, the potassium atom playing the role of internal chlorine sensor. Such compositions are, for example, described in patents FR-A-2 190 776 and FR-B-2 213 254 or in their US correspondents US-A-3,986,908 and US-A-3,964,256. However, these compositions exhibit the disadvantage of generating gases very rich in oxygen that are not wanted by the manufacturers of automobile industry.
Il existe aussi des compositions composites
constituées par un liant silicone et par un mélange de
perchlorate d'ammonium et de nitrate de sodium. De
telles compositions ne contiennent pas de solvant. Elles
sont par exemple décrites dans le brevet français
FR-A-2 728 562 ou dans son correspondant américain
US-A-5 610 444. Ces compositions génèrent bien des gaz
propres, riches en azote et non toxiques mais présentent
l'inconvénient de brûler à des températures très élevées
et de produire un taux de résidus solides élevé.
Les procédés de fabrication des compositions
existantes impliquent la présence d'un solvant pour
ajuster la viscosité. L'emploi d'un solvant présente de
nombreux inconvénients et notamment au niveau
industriel. Le solvant doit être éliminé de la
composition et cette opération risque de créer des
porosités dans le chargement pyrotechnique.There are also composite compositions constituted by a silicone binder and by a mixture of ammonium perchlorate and sodium nitrate. Such compositions do not contain a solvent. They are for example described in French patent FR-A-2 728 562 or in its American correspondent US-A-5 610 444. These compositions generate many clean gases, rich in nitrogen and non-toxic but have the drawback of burning at very high temperatures and produce a high solid residue level.
The methods of manufacturing existing compositions involve the presence of a solvent to adjust the viscosity. The use of a solvent has many drawbacks, especially at the industrial level. The solvent must be removed from the composition and this operation risks creating porosities in the pyrotechnic charge.
L'homme du métier est donc toujours à la recherche de compositions pyrotechniques génératrices de gaz, sans solvant, et qui génèrent à des températures acceptables pour l'industrie automobile des gaz propres, non toxiques, avec très peu de résidus solides. L'homme du métier est également à la recherche d'un procédé de fabrication continu de telles compositions, notamment sous forme de blocs.The skilled person is therefore always looking gas-generating pyrotechnic compositions, without solvent, and which generate at acceptable temperatures for the clean gas automotive industry, not toxic, with very little solid residue. The man of profession is also looking for a process for continuous manufacture of such compositions, in particular in the form of blocks.
L'objet de la présente invention est précisément de proposer de telles compositions ainsi qu'un procédé permettant de les mettre en oeuvre.The object of the present invention is precisely to propose such compositions and a method allowing to implement them.
L'invention concerne donc une composition
pyrotechnique génératrice de gaz comprenant un liant, un
composé organique azoté, des additifs et une charge
oxydante comprenant du perchlorate d'ammonium et un
capteur de chlore, ledit liant étant un liant
hydrocarboné à au moins deux composants, l'un des
composants étant constitué par une gomme, caractérisée
en ce que, lorsque la gomme est une gomme polyester,
elle est associée à une résine polyester et en ce que,
lorsque la gomme est une gomme acrylique, elle est
associée à un de ses plastifiants.
On appelle gomme un polymère dont la masse
moléculaire est supérieure à 200 000. Les gommes acryliques
utilisées sont aussi appelées caoutchoucs
acryliques ou polyacrylates. Ces gommes peuvent avoir
des terminaisons réactives de type chlore/carboxyle,
chlore, hydroxyl ou époxy.
Les gommes polyester utilisées sont des caoutchoucs
avec des motifs ester et qui peuvent avoir des
terminaisons réactives de type hydroxyl.The invention therefore relates to a gas-generating pyrotechnic composition comprising a binder, an organic nitrogen compound, additives and an oxidizing charge comprising ammonium perchlorate and a chlorine sensor, said binder being a hydrocarbon binder containing at least two components, one of the components being constituted by a gum, characterized in that, when the gum is a polyester gum, it is associated with a polyester resin and in that, when the gum is an acrylic gum, it is associated with one of its plasticizers.
A polymer whose molecular mass is greater than 200,000 is called gum. The acrylic gums used are also called acrylic rubbers or polyacrylates. These gums can have reactive terminations of the chlorine / carboxyl, chlorine, hydroxyl or epoxy type.
The polyester gums used are rubbers with ester units and which can have reactive hydroxyl type terminations.
On appelle résine un polymère hydrocarboné dont la masse moléculaire est comprise entre 100 et 10 000.Resin is a hydrocarbon polymer whose mass molecular is between 100 and 10,000.
Selon un premier mode préféré de réalisation, le
liant est constitué par l'association d'une gomme
acrylique et d'un de ses plastifiants. Le plastifiant de
la gomme acrylique est choisi dans le groupe constitué
par l'adipate de dioctyle et l'azélate de dioctyle.
Un réticulant sera généralement associé au liant.According to a first preferred embodiment, the binder is formed by the association of an acrylic gum and one of its plasticizers. The plasticizer for acrylic gum is chosen from the group consisting of dioctyl adipate and dioctyl azelate.
A crosslinker will generally be associated with the binder.
Selon un deuxième mode préféré de réalisation, le liant est constitué par l'association d'une gomme polyester et d'une résine polyester. Selon ce mode préféré de réalisation, la composition comprend en outre un réticulant de type isocyanate.According to a second preferred embodiment, the binder is formed by the association of an eraser polyester and polyester resin. According to this mode preferred embodiment, the composition further comprises an isocyanate crosslinker.
Selon un troisième mode préféré de réalisation, le teneur pondérale des charges est supérieure ou égale à 85% du poids total de la composition. On entend par charges à la fois les charges oxydantes, les composés organiques azotés et les autres additifs.According to a third preferred embodiment, the weight content of the charges is greater than or equal to 85% of the total weight of the composition. We hear by charges at the same time the oxidizing charges, the compounds organic nitrogen and other additives.
La charge oxydante comprend du perchlorate
d'ammonium et un capteur de chlore. Le capteur de chlore
est choisi dans le groupe constitué par le nitrate de
sodium, le carbonate de calcium, le carbonate de
lithium, le nitrate de potassium, le nitrate de
strontium, le nitrate de barium, le chlorate de
potassium, le perchlorate de potassium et l'oxyde de
cuivre.
Un capteur de chlore préféré est le nitrate de
sodium.The oxidizing charge includes ammonium perchlorate and a chlorine sensor. The chlorine sensor is chosen from the group consisting of sodium nitrate, calcium carbonate, lithium carbonate, potassium nitrate, strontium nitrate, barium nitrate, potassium chlorate, potassium perchlorate and copper oxide.
A preferred chlorine sensor is sodium nitrate.
La composition comprend également un composé organique azoté. Le composé organique azoté est choisi dans le groupe constitué par la nitroguanidine, le nitrate de guanidine, le nitrate d'aminoguanidine, l'oxamide, le dicyandiamide, le guanyluréedinitramide et les cyanamides métalliques. Préférentiellement la teneur pondérale de ce composé azoté est comprise entre 3 et 15% du poids total de la composition.The composition also includes a compound organic nitrogen. The organic nitrogen compound is chosen in the group consisting of nitroguanidine, the guanidine nitrate, aminoguanidine nitrate, oxamide, dicyandiamide, guanyluréedinitramide and metallic cyanamides. Preferably the content by weight of this nitrogen compound is between 3 and 15% of the total weight of the composition.
Selon un quatrième mode préféré de réalisation, la
composition comprend en outre un catalyseur balistique
choisi dans le groupe constitué par l'oxyde de titane,
l'oxyde de cuivre, le nitrate basique de cuivre, le
chromite de cuivre et l'oxyde de fer. Le catalyseur
balistique préféré est l'oxyde de fer. La teneur
pondérale du catalyseur balistique est
préférentiellement comprise entre 0% et 4% du poids
total de la composition.
Il permet entre autre d'améliorer la vitesse de
combustion.According to a fourth preferred embodiment, the composition also comprises a ballistic catalyst chosen from the group consisting of titanium oxide, copper oxide, basic copper nitrate, copper chromite and iron oxide . The preferred ballistic catalyst is iron oxide. The weight content of the ballistic catalyst is preferably between 0% and 4% of the total weight of the composition.
Among other things, it improves the combustion speed.
Selon un cinquième mode préféré de réalisation, la
composition comprend en outre un agent mouillant. Cet
agent mouillant est choisi dans le groupe constitué par
les organo-silanes, les titanates et les aziridines. Les
organo-silanes préférés sont les trialcoylsilanes dont
le groupe fonctionnel est un groupe vinyl, epoxy, amine
ou métacrylique.
La teneur pondérale de l'agent mouillant est
préférentiellement comprise entre 0,5% et 2% du poids
total de la composition.
Ce composant permet de réduire la porosité
résiduelle du produit.According to a fifth preferred embodiment, the composition further comprises a wetting agent. This wetting agent is chosen from the group consisting of organosilanes, titanates and aziridines. The preferred organosilanes are the trialkyl silanes in which the functional group is a vinyl, epoxy, amine or metacrylic group.
The weight content of the wetting agent is preferably between 0.5% and 2% of the total weight of the composition.
This component reduces the residual porosity of the product.
Le catalyseur balistique et l'agent mouillant constituent les additifs préférés des compositions selon l'invention.Ballistic catalyst and wetting agent constitute the preferred additives of the compositions according to the invention.
L'invention concerne également un procédé de fabrication continu et sans solvant dans un mélangeur-extrudeur bi-vis de telles compositions, caractérisé en ce que :
- le mélangeur-extrudeur bis-vis comprend un compartiment de mélange et de malaxage, un compartiment de compression et une tête d'extrusion, et en ce que,
- les constituants solides et liquides sont introduits dans le compartiment de mélange et de malaxage par deux ouvertures d'alimentation différentes, une ouverture d'alimentation des solides et une ouverture d'alimentation des liquides, et en ce qu'ils sont, dans ce compartiment, transportés et malaxés, puis, en ce que,
- la pâte homogène ainsi formée est dégazée dans le compartiment de compression puis extrudée, à l'aide d'une tête d'extrusion sous forme de joncs, et enfin en ce que,
- les joncs ainsi formés sont découpés en chargements à l'aide d'un appareil de découpe, et en ce que ces dits chargements sont mis à réticuler à une température comprise entre 100°C et 150°C.
- the twin-screw mixer-extruder comprises a mixing and kneading compartment, a compression compartment and an extrusion head, and in that,
- the solid and liquid constituents are introduced into the mixing and kneading compartment by two different supply openings, a solid supply opening and a liquid supply opening, and in that they are, in this compartment , transported and kneaded, then, in that,
- the homogeneous paste thus formed is degassed in the compression compartment and then extruded, using an extrusion head in the form of rods, and finally in that,
- the rods thus formed are cut into loads using a cutting device, and in that these said loads are crosslinked at a temperature between 100 ° C and 150 ° C.
Selon une variante préférée de l'invention, le composé organique azoté et la gomme sont prémélangés et introduits dans le compartiment de mélange et de malaxage par l'ouverture d'alimentation des solides.According to a preferred variant of the invention, the organic nitrogen compound and gum are premixed and introduced into the mixing compartment and mixing through the solids feed opening.
Selon une autre variante préférée de l'invention, la pression du compartiment de compression est inférieure à 50.103 Pa, soit 500 mbar.According to another preferred variant of the invention, the pressure of the compression compartment is less than 50 × 10 3 Pa, ie 500 mbar.
La température du compartiment de mélange et de malaxage est comprise entre 15°C et 75°C.The temperature of the mixing compartment and mixing is between 15 ° C and 75 ° C.
La pression dans la tête d'extrusion est comprise entre 6.106Pa et 15.106Pa, soit entre 60 bars et 150 bars. The pressure in the extrusion head is between 6.10 6 Pa and 15.10 6 Pa, ie between 60 bars and 150 bars.
L'originalité fondamentale de l'invention réside
dans le fait que le liant hydrocarboné comprend d'une
part une gomme et d'autre part un constituant liquide
qui est soit une résine, soit un plastifiant. On obtient
donc un liant pâteux. Quand on incorpore à ce liant la
charge oxydante, le composé organique azoté et les
divers additifs, ce liant a suffisamment de tenue pour
être extrudé sous forme de joncs. Il n'y a donc besoin
ni d'agent épaississant, ni de solvant.
Les joncs sont ensuite découpés en chargements et
la structure du liant est définitivement figée par
réticulation en étuve à une température comprise entre
100°C et 150°C.The fundamental originality of the invention lies in the fact that the hydrocarbon binder comprises on the one hand a gum and on the other hand a liquid constituent which is either a resin or a plasticizer. A pasty binder is therefore obtained. When the oxidizing charge, the nitrogenous organic compound and the various additives are incorporated into this binder, this binder has sufficient strength to be extruded in the form of rods. There is therefore no need for a thickening agent or a solvent.
The rods are then cut into loads and the structure of the binder is definitively frozen by crosslinking in an oven at a temperature between 100 ° C and 150 ° C.
On donne maintenant une description détaillée du mode préféré de réalisation de l'invention en se référant à la figure 1 qui représente, sous forme de schéma partiellement coupé, une installation permettant la mise en oeuvre du procédé selon l'invention.We now give a detailed description of the preferred embodiment of the invention by referring to Figure 1 which represents, in the form of partially cut diagram, an installation allowing the implementation of the method according to the invention.
L'extrudeur-malaxeur bis-vis 1 comprend une partie
amont 2 dans laquelle se situent les opérations de
mélange et de malaxage de la composition, une partie
aval 3 dans laquelle a lieu l'opération de dégazage de
la composition et une tête d'extrusion 4.
En cours de fonctionnement, il se forme un bouchon
de matière qui sépare la partie aval 2 de la partie
amont 3.
Dans la suite de la présente description, on
appellera la partie amont 2 « compartiment de mélange et
de malaxage » et la partie aval 3 « compartiment de
compression ».The twin-screw extruder-mixer 1 comprises an
During operation, a plug of material is formed which separates the
In the remainder of this description, the
La gomme et le composé organique azoté sont prémélangés. The gum and the nitrogenous organic compound are premixed.
Préférentiellement la gomme sera une gomme acrylique et le composé azoté sera du nitrate de guanidine.Preferably the eraser will be an eraser acrylic and the nitrogen compound will be nitrate of guanidine.
En phase de démarrage, on introduit d'abord les
constituants inertes, à savoir le plastifiant et les
divers additifs. On introduit ensuite les charges
oxydantes et le mélange gomme/composé organique azoté.
Une fois la phase de démarrage terminée, les divers
constituants sont introduits en continu dans le
compartiment de mélange et de malaxage. Les solides A
sont introduits sans solvant au moyen d'une trémie. Les
liquides B sont introduits sans solvant au moyen d'une
pompe doseuse 6. Les liquides B sont constitués par le
plastifiant et l'agent mouillant. Les solides A sont le
mélange gomme acrylique/nitrate de guanidine, la charge
oxydante comprenant du perchlorate d'ammonium et les
additifs autres que l'agent mouillant.
On utilise des particules de perchlorate d'ammonium
de deux granulométries différentes. La granulométrie est
comprise entre 10µm et 50µm.
Le perchlorate d'ammonium produisant par combustion
des dérivés chlorés, il lui est adjoint un capteur de
chlore. Le capteur de chlore préféré dans le cadre de
l'invention est le nitrate de sodium qui fixe le chlore
sous forme de chlorure de sodium de taille
submicronique, donc sans risque de détérioration des
parois du coussin gonflable.
Le nitrate de sodium sera également introduit par
l'ouverture d'alimentation des solides A. Le ratio entre
le perchlorate d'ammonium et le nitrate de sodium est
compris entre 1 et 2.
Le taux de charges oxydantes est préférentiellement
d'environ 80% du poids total de la composition, pour
avoir une composition assez équilibrée en balance en
oxygène. In the start-up phase, the inert constituents, namely the plasticizer and the various additives, are first introduced. The oxidizing charges and the gum / nitrogenous organic compound mixture are then introduced. Once the start-up phase is complete, the various constituents are continuously introduced into the mixing and kneading compartment. Solids A are introduced without solvent by means of a hopper. The liquids B are introduced without solvent by means of a metering pump 6. The liquids B consist of the plasticizer and the wetting agent. Solids A are the acrylic gum / guanidine nitrate mixture, the oxidizing charge comprising ammonium perchlorate and the additives other than the wetting agent.
Particles of ammonium perchlorate of two different particle sizes are used. The particle size is between 10 μm and 50 μm.
Since ammonium perchlorate produces chlorine derivatives by combustion, it has a chlorine sensor attached to it. The preferred chlorine sensor in the context of the invention is sodium nitrate which fixes the chlorine in the form of sodium chloride of submicron size, therefore without risk of damaging the walls of the airbag.
Sodium nitrate will also be introduced through the feed opening for solids A. The ratio between ammonium perchlorate and sodium nitrate is between 1 and 2.
The rate of oxidizing charges is preferably around 80% of the total weight of the composition, to have a composition fairly balanced in oxygen balance.
La teneur pondérale des charges (c'est-à-dire
charge oxydante, composé organique azoté et additifs)
est supérieure ou égale à 85% du poids total de la
composition. Ce sont donc des compositions à liant
fortement chargé. La teneur de la composition en liant
et réticulant sera avantageusement voisine de 15%.
Les additifs préférés sont l'agent mouillant et le
catalyseur balistique. Le catalyseur balistique préféré
est l'oxyde de fer.
Les constituants sont transportés et malaxés dans
le compartiment de mélange et de malaxage 2. Les
constituants sont malaxés au moyen des éléments de
malaxage 7 de manière à former une pâte homogène. La
température au sein de ce compartiment est comprise
entre 15°C et 75°C.The weight content of the fillers (that is to say oxidizing charge, nitrogenous organic compound and additives) is greater than or equal to 85% of the total weight of the composition. They are therefore compositions with a highly charged binder. The content of the binder and crosslinker composition will advantageously be close to 15%.
The preferred additives are the wetting agent and the ballistic catalyst. The preferred ballistic catalyst is iron oxide.
The constituents are transported and kneaded in the mixing and kneading
La pâte formée dans le compartiment de mélange et
de malaxage 2 est ensuite dégazée dans le compartiment
de compression 3, sous une pression inférieure à
30.103Pa, soit 300 mbar.
Cette pâte est ensuite extrudée, au moyen d'une
tête d'extrusion 4, sous forme de joncs 8. La pression
dans la tête d'extrusion est de préférence voisine de
100 bars.
Ces joncs sont alors découpés en chargements 9 à
l'aide d'un appareil de découpe 10. Ces chargements 9
sont récupérés par un tapis transporteur 11 et acheminés
vers une étuve 12. Cette étuve 12 est chauffée à une
température comprise entre 100 et 150°C. De préférence,
cette étuve est chauffée à 120°C. Les chargements
restent 3 heures environ dans cette étuve de manière à
achever la réticulation des constituants du liant et à
figer ainsi la structure des chargements 9.The paste formed in the mixing and kneading
This paste is then extruded, by means of an extrusion head 4, in the form of rods 8. The pressure in the extrusion head is preferably close to 100 bars.
These rods are then cut into loads 9 using a
De façon particulièrement préférée les chargements
9 ont la forme de blocs cylindriques creux présentant le
plus souvent des canaux axiaux.
Les chargements ainsi formés trouvent leur
application préférentielle comme chargement
pyrotechnique dans les générateurs de gaz destinés à
gonfler un coussin de protection pour occupants d'un
véhicule automobile. En effet, la vitesse de combustion
de ces chargements, ainsi que le taux de résidus solides
produits et le taux de monoxyde de carbone et d'oxydes
d'azote produits conviennent particulièrement bien aux
exigences de la sécurité automobile.
Les exemples qui suivent illustrent, à titre non
limitatif, certaines possibilités de mise en oeuvre de
l'invention.In a particularly preferred manner, the loads 9 have the form of hollow cylindrical blocks most often having axial channels.
The charges thus formed find their preferred application as pyrotechnic charges in gas generators intended to inflate a protective cushion for occupants of a motor vehicle. In fact, the rate of combustion of these loads, as well as the rate of solid residues produced and the rate of carbon monoxide and nitrogen oxides produced are particularly suitable for the requirements of automobile safety.
The examples which follow illustrate, without limitation, certain possibilities of implementing the invention.
On a fabriqué selon le procédé représenté à la figure 1 la composition génératrice de gaz suivante :
- gomme acrylique : 5,5% du poids total de la composition
- plastifiant (adipate de dioctyle ou azélate de dioctyle) : 6,5% du poids total de la composition.
- acrylic gum: 5.5% of the total weight of the composition
- plasticizer (dioctyl adipate or dioctyl azelate): 6.5% of the total weight of the composition.
La teneur en liant est donc de 12% du poids total de la composition.
- perchlorate d'ammonium bigranulométrique n'exédant pas 50µm : 60,5% en poids, le perchlorate fin étant en excès pondéral par rapport au perchlorate de plus grosse granulométrie.
- nitrate de sodium : 20% en poids
- bigranulometric ammonium perchlorate not exceeding 50 μm: 60.5% by weight, the fine perchlorate being in excess in weight with respect to the larger particle size perchlorate.
- sodium nitrate: 20% by weight
La teneur en charges oxydantes est de 80,5% en poids.
- nitrate de guanidine : 5% en poids
- oxyde de fer : 1,5% en poids
- agent mouillant (vinyl silane) : 1% en poids
- guanidine nitrate: 5% by weight
- iron oxide: 1.5% by weight
- wetting agent (vinyl silane): 1% by weight
La teneur pondérale des charges est de 88%.
La température de combustion de cette composition
est de l'ordre de 2400°C.
La vitesse de combustion est de 33mm/s sous 20 Mpa.
Les caractéristiques des gaz de combustion de 18g
d'une telle composition sont les suivantes :
- teneur globale des gaz en résidus solides à la température de combustion : 15,5%
- teneur des gaz en monoxyde de carbone, pour un volume de 60 L : 4500 ppm
- teneur des gaz en oxydes d'azote, pour un volume de 60 L : 1000 ppm.
The combustion temperature of this composition is of the order of 2400 ° C.
The combustion speed is 33mm / s at 20 Mpa.
The characteristics of the 18g combustion gases of such a composition are as follows:
- overall content of gases in solid residues at combustion temperature: 15.5%
- carbon monoxide content of the gases, for a volume of 60 L: 4500 ppm
- nitrogen oxide content of the gases, for a volume of 60 L: 1000 ppm.
On a fabriqué selon le procédé représenté à la figure 1 la composition génératrice de gaz suivante :
- gomme acrylique : 6,6% du poids total de la composition
- plastifiant (adipate de dioctyle ou azélate de
dioctyle) : 5,5% du poids total de la
composition.
La teneur en liant est donc de 12,1 % du poids total de la composition - perchlorate d'ammonium bigranulométrique n'excédant pas 50µm : 58,5% en poids, le perchlorate de plus grosse granulométrie étant en excès par rapport au perchlorate fin.
- nitrate de sodium : 15,9% en poids
- nitrate basique de cuivre : 6,5% en poids.
La teneur en charges oxydantes est de 80,9% en poids - agent mouillant (vinyl silane) : 1% en poids
- nitrate de guanidine : 6% en poids
- acrylic gum: 6.6% of the total weight of the composition
- plasticizer (dioctyl adipate or dioctyl azelate): 5.5% of the total weight of the composition.
The binder content is therefore 12.1% of the total weight of the composition - bigranulometric ammonium perchlorate not exceeding 50 μm: 58.5% by weight, the perchlorate of larger particle size being in excess relative to the fine perchlorate.
- sodium nitrate: 15.9% by weight
- basic copper nitrate: 6.5% by weight.
The content of oxidizing charges is 80.9% by weight - wetting agent (vinyl silane): 1% by weight
- guanidine nitrate: 6% by weight
La teneur pondérale des charges est de 87,9%The weight content of the fillers is 87.9%
La température de combustion de cette composition
est de l'ordre de 2400°C .
La vitesse de combustion est de 43mm/s sous 20 Mpa.
Les caractéristiques des gaz de combustion de 18g
d'une telle composition sont les suivantes :
- teneur globale des gaz en résidus solides à la température de combustion : 14,6%
- teneur des gaz en monoxyde de carbone, pour un volume de 60L : 4500ppm
- teneur des gaz en oxydes d'azote, pour un volume de 60L : 1000ppm.
The combustion speed is 43mm / s at 20 Mpa.
The characteristics of the 18g combustion gases of such a composition are as follows:
- overall content of gases in solid residues at combustion temperature: 14.6%
- carbon monoxide content of the gases, for a volume of 60L: 4500ppm
- nitrogen oxides content of the gases, for a volume of 60L: 1000ppm.
On a fabriqué selon le procédé représenté à la figure 1 la composition génératrice de gaz suivante :
- gomme polyester : 3,46% en poids
- résine polyester : 8,76% en poids
- agent réticulant (méthylène dicyclohexyl diisocyanate) : 2,78% en poids
- polyester gum: 3.46% by weight
- polyester resin: 8.76% by weight
- crosslinking agent (methylene dicyclohexyl diisocyanate): 2.78% by weight
La teneur en liant et en réticulant est donc de 15% en poids
- perchlorate d'ammonium bigranulométrique n'excédant pas 50 µm : 54% en poids, le perchlorate de plus grosse granulométrie étant en excès par rapport au perchlorate fin
- nitrate de sodium : 15,5% en poids
- oxyde de cuivre : 7% en poids
- bigranulometric ammonium perchlorate not exceeding 50 µm: 54% by weight, the perchlorate of larger particle size being in excess relative to the fine perchlorate
- sodium nitrate: 15.5% by weight
- copper oxide: 7% by weight
La teneur en charges oxydantes est de 76,5% en poids
- nitrate de guanidine : 8,5% en poids
- guanidine nitrate: 8.5% by weight
La teneur pondérale des charges est de 85%. The weight content of the fillers is 85%.
La température de combustion de cette composition
est de l'ordre de 2400°C.
La vitesse de combustion est de 20mm/s sous 20Mpa.
Les caractéristiques des gaz de combustion de 18g
d'une telle composition sont les suivantes :
- teneur globale des gaz en résidus solides à la température de combustion : 16,3%
- teneur des gaz en monoxyde de carbone, pour un volume de 60L : 4500ppm
- teneur des gaz en oxydes d'azote, pour un volume de 60L : 800ppm.
The combustion speed is 20mm / s under 20Mpa.
The characteristics of the 18g combustion gases of such a composition are as follows:
- overall content of gases in solid residues at combustion temperature: 16.3%
- carbon monoxide content of the gases, for a volume of 60L: 4500ppm
- nitrogen oxides content of the gases, for a volume of 60L: 800ppm.
Claims (14)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0016879A FR2818636B1 (en) | 2000-12-22 | 2000-12-22 | HYDROCARBON BINDER GAS GENERATING PYROTECHNIC COMPOSITIONS AND CONTINUOUS MANUFACTURING METHOD |
| FR0016879 | 2000-12-22 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP1216977A2 true EP1216977A2 (en) | 2002-06-26 |
| EP1216977A3 EP1216977A3 (en) | 2002-09-11 |
| EP1216977B1 EP1216977B1 (en) | 2005-07-27 |
Family
ID=8858087
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP01403255A Expired - Lifetime EP1216977B1 (en) | 2000-12-22 | 2001-12-14 | Hydrocarbon binder containing pyrotechnic gas-generating compositions and method for continuous manufacturing |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US6824626B2 (en) |
| EP (1) | EP1216977B1 (en) |
| JP (1) | JP3825316B2 (en) |
| KR (1) | KR100446267B1 (en) |
| AT (1) | ATE300508T1 (en) |
| BR (1) | BR0106250B1 (en) |
| CA (1) | CA2364135C (en) |
| DE (1) | DE60112231T2 (en) |
| FR (1) | FR2818636B1 (en) |
| MX (1) | MXPA01012981A (en) |
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|---|---|---|---|---|
| FR2857359A1 (en) * | 2003-07-10 | 2005-01-14 | Snpe Materiaux Energetiques | GAS GENERATING PYROTECHNIC COMPOSITION FOR MOTOR VEHICLE SAFETY AND BURNING AT COMBUSTION TEMPERATURES LESS THAN 2200 K |
| EP1553071A2 (en) * | 2004-01-12 | 2005-07-13 | TRW Airbag Systems GmbH | Method of inflating an airbag and airbag module for use in this method |
| FR2902783A1 (en) * | 2006-06-27 | 2007-12-28 | Snpe Materiaux Energetiques Sa | THERMO-INITIABLE PYROTECHNIC COMPOSITIONS, USE |
| FR2915746A1 (en) * | 2007-05-02 | 2008-11-07 | Snpe Materiaux Energetiques Sa | PYROTECHNIC COMPOUND GAS GENERATOR; PROCESS FOR OBTAINING |
| FR2950624A1 (en) * | 2009-09-25 | 2011-04-01 | Snpe Materiaux Energetiques | Pyrotechnic compound comprising ammonium perchlorate oxidative charge, nitrogenous organic charge of at least one compound comprising e.g. triazoles and metal oxide charge, useful in gas generator for airbag and inflate cushioning pillows |
| WO2011135262A1 (en) | 2010-04-29 | 2011-11-03 | Sme | Gas-generating pyrotechnic compound and production process |
| WO2013045804A1 (en) | 2011-09-26 | 2013-04-04 | Herakles | Method for extracting solid soluble fillers contained in a paste |
| US10159861B2 (en) | 2013-06-28 | 2018-12-25 | Arianegroup Sas | Method for delivering a liquid pressurised by the combustion gases from at least one pyrotechnic charge |
| WO2019063923A1 (en) * | 2017-09-29 | 2019-04-04 | Arianegroup Sas | Gas-generating composition |
| EP3770136A1 (en) * | 2019-07-25 | 2021-01-27 | ArianeGroup SAS | Composite solid propellant |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040094250A1 (en) * | 2002-11-14 | 2004-05-20 | Estes-Cox Corporation | Composite propellant compositions |
| US20050016646A1 (en) * | 2003-07-25 | 2005-01-27 | Barnes Michael W. | Chlorine-containing gas generant compositions including a copper-containing chlorine scavenger |
| WO2007012348A1 (en) * | 2005-07-26 | 2007-02-01 | Dalphi Metal España, S.A. | Gas generating composition for automotive use manufactured by pellet formation |
| US7857920B1 (en) * | 2005-08-22 | 2010-12-28 | The United States Of America As Represented By The Secretary Of The Navy | Low temperature clean burning pyrotechnic gas generators |
| US8778104B1 (en) * | 2008-04-22 | 2014-07-15 | The United States Of America As Represented By The Secretary Of The Navy | Insensitive gun propellant, ammunition round assembly, armament system, and related methods |
| DE102009049003A1 (en) * | 2009-10-09 | 2011-06-16 | Rheinmetall Waffe Munition Gmbh | Plastic-bound pyrotechnic mixture for the production of alkali metal chloride or alkaline earth metal chloride aerosols as camouflage mist |
| DE102011100113B4 (en) | 2010-06-28 | 2019-10-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Gas generator fuel composition, process for its preparation and its use |
| RU2496753C2 (en) * | 2011-04-08 | 2013-10-27 | Открытое акционерное общество "Научно-производственное предприятие "Краснознамёнец" | Method of producing gas-generating pyrotechnic compound with polymer binder |
| FR2975097B1 (en) * | 2011-05-09 | 2015-11-20 | Sme | PYROTECHNIC COMPOUNDS GENERATORS OF GAS |
| FR3073775B1 (en) * | 2017-11-23 | 2020-12-25 | Arianegroup Sas | EXTRUSION PLANT EQUIPPED WITH A CONTROL SYSTEM SUITABLE TO DETECT ANY ANOMALY |
| DE102019218387B4 (en) * | 2019-11-27 | 2021-12-09 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Measuring arrangement and method for determining the properties of a material to be extruded while a screw extrusion process is being carried out |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2857359A1 (en) * | 2003-07-10 | 2005-01-14 | Snpe Materiaux Energetiques | GAS GENERATING PYROTECHNIC COMPOSITION FOR MOTOR VEHICLE SAFETY AND BURNING AT COMBUSTION TEMPERATURES LESS THAN 2200 K |
| EP1553071A2 (en) * | 2004-01-12 | 2005-07-13 | TRW Airbag Systems GmbH | Method of inflating an airbag and airbag module for use in this method |
| EP1553071A3 (en) * | 2004-01-12 | 2013-04-24 | TRW Airbag Systems GmbH | Method of inflating an airbag and airbag module for use in this method |
| FR2902783A1 (en) * | 2006-06-27 | 2007-12-28 | Snpe Materiaux Energetiques Sa | THERMO-INITIABLE PYROTECHNIC COMPOSITIONS, USE |
| WO2008001005A2 (en) * | 2006-06-27 | 2008-01-03 | Snpe Materiaux Energetiques | Pyrotechnic compositions initiable by heat, and their use |
| WO2008001005A3 (en) * | 2006-06-27 | 2008-02-28 | Snpe Materiaux Energetiques | Pyrotechnic compositions initiable by heat, and their use |
| CN101679139B (en) * | 2007-05-02 | 2012-09-26 | Snpe巨能材料公司 | Gas-generating pyrotechnic compound and production process |
| FR2915746A1 (en) * | 2007-05-02 | 2008-11-07 | Snpe Materiaux Energetiques Sa | PYROTECHNIC COMPOUND GAS GENERATOR; PROCESS FOR OBTAINING |
| WO2008145935A2 (en) | 2007-05-02 | 2008-12-04 | Snpe Materiaux Energetiques | Gas-generating pyrotechnic compound and production process. |
| WO2008145935A3 (en) * | 2007-05-02 | 2009-09-17 | Snpe Materiaux Energetiques | Gas-generating pyrotechnic compound and production process. |
| FR2950624A1 (en) * | 2009-09-25 | 2011-04-01 | Snpe Materiaux Energetiques | Pyrotechnic compound comprising ammonium perchlorate oxidative charge, nitrogenous organic charge of at least one compound comprising e.g. triazoles and metal oxide charge, useful in gas generator for airbag and inflate cushioning pillows |
| FR2959508A1 (en) * | 2010-04-29 | 2011-11-04 | Snpe Materiaux Energetiques | PYROTECHNIC COMPOUND GAS GENERATOR; PROCESS FOR OBTAINING |
| WO2011135262A1 (en) | 2010-04-29 | 2011-11-03 | Sme | Gas-generating pyrotechnic compound and production process |
| WO2013045804A1 (en) | 2011-09-26 | 2013-04-04 | Herakles | Method for extracting solid soluble fillers contained in a paste |
| US9393503B2 (en) | 2011-09-26 | 2016-07-19 | Herakles | Method for extracting solid soluble charges contained in a paste |
| US10159861B2 (en) | 2013-06-28 | 2018-12-25 | Arianegroup Sas | Method for delivering a liquid pressurised by the combustion gases from at least one pyrotechnic charge |
| WO2019063923A1 (en) * | 2017-09-29 | 2019-04-04 | Arianegroup Sas | Gas-generating composition |
| FR3071831A1 (en) * | 2017-09-29 | 2019-04-05 | Arianegroup Sas | GAS GENERATING COMPOSITION |
| EP3770136A1 (en) * | 2019-07-25 | 2021-01-27 | ArianeGroup SAS | Composite solid propellant |
| FR3099155A1 (en) * | 2019-07-25 | 2021-01-29 | Arianegroup Sas | SOLID COMPOSITE PROPERGOL |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2364135C (en) | 2009-02-03 |
| BR0106250B1 (en) | 2010-11-16 |
| DE60112231T2 (en) | 2006-05-24 |
| FR2818636A1 (en) | 2002-06-28 |
| KR20020051850A (en) | 2002-06-29 |
| US6824626B2 (en) | 2004-11-30 |
| US20020079031A1 (en) | 2002-06-27 |
| MXPA01012981A (en) | 2002-10-21 |
| EP1216977B1 (en) | 2005-07-27 |
| BR0106250A (en) | 2002-08-13 |
| CA2364135A1 (en) | 2002-06-22 |
| ATE300508T1 (en) | 2005-08-15 |
| KR100446267B1 (en) | 2004-09-01 |
| DE60112231D1 (en) | 2005-09-01 |
| FR2818636B1 (en) | 2003-02-28 |
| JP2002255679A (en) | 2002-09-11 |
| EP1216977A3 (en) | 2002-09-11 |
| JP3825316B2 (en) | 2006-09-27 |
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