EP0576326B1 - Pyrotechnic composition, which generates a hot non-toxic gas and use thereof in a protection system for motor vehicle occupants - Google Patents
Pyrotechnic composition, which generates a hot non-toxic gas and use thereof in a protection system for motor vehicle occupants Download PDFInfo
- Publication number
- EP0576326B1 EP0576326B1 EP93401513A EP93401513A EP0576326B1 EP 0576326 B1 EP0576326 B1 EP 0576326B1 EP 93401513 A EP93401513 A EP 93401513A EP 93401513 A EP93401513 A EP 93401513A EP 0576326 B1 EP0576326 B1 EP 0576326B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- composition
- compositions
- use according
- combustion
- 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.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 77
- 231100000252 nontoxic Toxicity 0.000 title description 2
- 230000003000 nontoxic effect Effects 0.000 title description 2
- 239000002341 toxic gas Substances 0.000 title 1
- 238000002485 combustion reaction Methods 0.000 claims description 25
- 239000011230 binding agent Substances 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 17
- 239000004014 plasticizer Substances 0.000 claims description 15
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 14
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 4
- ZQXWPHXDXHONFS-UHFFFAOYSA-N 1-(2,2-dinitropropoxymethoxy)-2,2-dinitropropane Chemical compound [O-][N+](=O)C([N+]([O-])=O)(C)COCOCC(C)([N+]([O-])=O)[N+]([O-])=O ZQXWPHXDXHONFS-UHFFFAOYSA-N 0.000 claims description 3
- SIKUYNMGWKGHRS-UHFFFAOYSA-N 1-[1-(2,2-dinitropropoxy)ethoxy]-2,2-dinitropropane Chemical compound [O-][N+](=O)C(C)([N+]([O-])=O)COC(C)OCC(C)([N+]([O-])=O)[N+]([O-])=O SIKUYNMGWKGHRS-UHFFFAOYSA-N 0.000 claims description 3
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 3
- XPAYEWBTLKOEDA-UHFFFAOYSA-N 3-methyl-4-nitroaniline Chemical compound CC1=CC(N)=CC=C1[N+]([O-])=O XPAYEWBTLKOEDA-UHFFFAOYSA-N 0.000 claims description 3
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- AGCQZYRSTIRJFM-UHFFFAOYSA-N triethylene glycol dinitrate Chemical compound [O-][N+](=O)OCCOCCOCCO[N+]([O-])=O AGCQZYRSTIRJFM-UHFFFAOYSA-N 0.000 claims description 3
- IPPYBNCEPZCLNI-UHFFFAOYSA-N trimethylolethane trinitrate Chemical compound [O-][N+](=O)OCC(C)(CO[N+]([O-])=O)CO[N+]([O-])=O IPPYBNCEPZCLNI-UHFFFAOYSA-N 0.000 claims description 3
- 150000001540 azides Chemical class 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims 2
- RDLIBIDNLZPAQD-UHFFFAOYSA-N 1,2,4-butanetriol trinitrate Chemical compound [O-][N+](=O)OCCC(O[N+]([O-])=O)CO[N+]([O-])=O RDLIBIDNLZPAQD-UHFFFAOYSA-N 0.000 claims 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000000567 combustion gas Substances 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 239000000020 Nitrocellulose Substances 0.000 description 4
- 230000001419 dependent effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229920001220 nitrocellulos Polymers 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- -1 aluminum or boron Chemical class 0.000 description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000013638 trimer Substances 0.000 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 description 2
- 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 description 2
- JSOGDEOQBIUNTR-UHFFFAOYSA-N 2-(azidomethyl)oxirane Chemical compound [N-]=[N+]=NCC1CO1 JSOGDEOQBIUNTR-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000000028 HMX Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- BSPUVYFGURDFHE-UHFFFAOYSA-N Nitramine Natural products CC1C(O)CCC2CCCNC12 BSPUVYFGURDFHE-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical compound [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 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 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N N-phenyl aniline Natural products C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 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
- 206010039203 Road traffic accident Diseases 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- FBYUNLMTXMFAQK-UHFFFAOYSA-N butyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCCC.CCCCCCCCCCCC(=O)OCCCC FBYUNLMTXMFAQK-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229960003711 glyceryl trinitrate Drugs 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000926 not very toxic Toxicity 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 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
- 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
Definitions
- the present invention relates to the field of automobile safety. More specifically, the invention relates to the protection, in the event of a collision, of the occupants of a motor vehicle by means of a bag which is inflated by gases originating from the combustion of a pyrotechnic composition.
- the invention relates to a composition generating non-toxic hot gases mainly consisting of an inorganic oxidant and a binder based on poly (glycidyl azide).
- compositions mainly generating, by combustion, nitrogen are favorite. These compositions generally consist of an alkali or alkaline earth azide and an oxidant. Such compositions are, for example, described in US Patents 3741585, 4203787 or 4547235. These compositions generate so-called "cold" gases whose temperature at the outlet of the combustion chamber is generally between 600 ° C and 800 ° C but which contain solid residues which must be filtered before the gases enter the bag. Such compositions require the use of complex generators, comprising one or more filtration and cooling chambers. Furthermore, these compositions have poor mechanical strength.
- pyrotechnic composition compositions based on nitrocellulose, optionally plasticized with nitroglycerin, which have the advantage of generating no solid residue and allow the use of very simple generators consisting essentially of an igniter and a combustion chamber without any filtration chamber.
- these nitrocellulose-based compositions have other drawbacks.
- the combustion gases of these compositions have a relatively high content of toxic products, in particular carbon monoxide, which means that certain motor vehicle manufacturers are reluctant to use protective devices using these compositions.
- the combustion speed of these compositions very much depends on the pressure prevailing in the combustion chamber, the curve representing the combustion speed of such a composition as a function of the pressure having no "plateau" in the operating zone. .
- the compositions of this type known to date cannot be used in the automobile safety devices mentioned above due to the toxicity of their combustion gases or the presence, in the latter, of hot solid residues.
- US Pat. No. 5,074,938 describes propellants for self-propulsion constituted mainly by a binder of the polyadipate glycol type, by an energy plasticizer of this binder, by ammonium nitrate and by boron particles.
- a binder of the polyadipate glycol type by an energy plasticizer of this binder, by ammonium nitrate and by boron particles.
- Such a composition does indeed have a "plateau" effect with a curve of the combustion rate as a function of the pressure which reveals a low pressure exponent, but the gases generated are, by the very nature of the binder, rich in carbon monoxide and moreover they contain solid particles of boron.
- gases generated cannot be used, without a filtration device, to inflate a safety cushion for a motor vehicle.
- US Pat. No. 4,938,813 illustrates another type of such compositions which are mainly constituted by a binder based on glycidyl polyazide and by an oxidizing charge which is a nitramine such as hexogen or octogen.
- Compositions of this type have although a "plateau" effect with a combustion speed relatively little dependent on the pressure, but the presence of nitramines leads to a high toxicity of the combustion gases incompatible with the standards required for automobile safety. Furthermore, these compositions often contain lead additives which generate solid residues as additives.
- Application WO 89/03372 describes similar compositions containing a metal such as aluminum and a “neutral” polymerized organic compound ensuring better cohesion of the charges.
- compositions are mainly constituted by a binder based on a copolymer of polyazide of glycidyl and polyepoxide and by a mineral filler which is either nitrate of ammonium, or ammonium perchlorate. These compositions do not have a marked plateau effect and, moreover, the presence of polyepoxide units in the binder results in a significant content in the combustion gases of toxic products, in particular carbon monoxide.
- pyrotechnic compositions generating by combustion hot gases which are not very toxic, the combustion rate of which is not very dependent on the pressure in the field of use which is usually between 100 and 500 bars. , that is to say between 10 and 50 MPa (Méga Pascal), and finally which burn without solid residues.
- the object of the present invention is to provide a person skilled in the art with pyrotechnic compositions which generate hot gases which meet the requirements set out above without having the drawbacks which arise. to be mentioned.
- the compositions contain at least one additive chosen from the group consisting of ammonium perchlorate, carbon black and m-methyl p-nitro aniline.
- the weight content of additive represents up to 3% by weight of the total weight of the composition, the weight content of the energy binder / plasticizer assembly being between 30 and 40% by weight of the total weight of the composition while the weight content of the whole oxidizing charge / additives is between 70% and 60% by weight of the total weight of the composition.
- the said energy plasticizer is chosen from the group consisting of butane triol 1,2,4 trinitrate, trimethylolethane trinitrate, triethylene glycol dinitrate, bis (2,2 dinitropropyl) acetal, bis (2,2 dinitropropyl) formal.
- compositions thus defined burn, essentially giving off nitrogen without producing solid residues.
- these compositions have combustion rates that are not very dependent on pressure between 150 and 500 bars, ie between 15 and 50 MPa (Mega Pascal) and of a value compatible with the requirements of automotive safety.
- These compositions therefore prove to be particularly well suited for pyrotechnic gas generators intended to inflate, in the event of a motor vehicle accident, protective cushions, and in particular they are well suited to generators without a filtration device which are very exposed to falling. sudden pressure caused by the sudden deployment of the airbag.
- a composition which can be used in the context of the invention essentially comprises, as indicated above, a binder, an energetic plasticizer, an oxidizing charge and optionally additives.
- the binder consists of the reaction product of a glycidyl polyazide with OH hydroxyl endings with at least one polyisoyanate.
- the glycidyl polyazides with OH hydroxyl endings which can be used in the context of the present invention are polyethers of general formula: in which C, H, O, N represent carbon, hydrogen, oxygen and nitrogen respectively and where n represents an integer between 5 and 100.
- polymers are generally obtained by reaction of sodium azide on a polyepichlorohydrin as described for example in US Patents 4,268,450, 4,379,894 or 4,486,351.
- glycidyl polyazides with a molecular weight will be used between 600 and 7000 and we prefer those whose molecular mass is between 1500 and 2500.
- polyisocyanate aliphatic, cycloaliphatic or usual aromatics such as, for example, methyl-1 cyclohexane-2,4 diisocyanate, methyl-1 cyclohexane-2,6 diisocyanate, dicyclohexylmethane-4,4 'diisocyanate, isophorone diisocyanate, methylene diisocyanate, hexane-1 , 6 diisocyanate, trimethyl-2, 2,4 hexane-1,6 diisocyanate, toluene diisocyanate, the biuret trimer of hexamethylene diisocyanate, polymethylene polyphenyl isocyanate.
- aromatics such as, for example, methyl-1 cyclohexane-2,4 diisocyanate, methyl-1 cyclohexane-2,6 diisocyanate, dicyclohexylmethane-4,4 'diisocyanate, isophor
- trimer biuret of hexamethylene diisocyanate of formula: polyisocyanate is preferred: and polymethylene polyphenylisocyanates of formula: in which x represents an integer or zero and which have an average NCO group functionality of 2.7.
- the NCO: OH ratio is close to 1: 1.
- the isocyanate In order to improve the three-dimensional crosslinking of the binder, it is possible to add to the isocyanate a little of a short triol such as, for example, trimethylolpropane.
- the composition contains an energetic plasticizer for the binder.
- the preferred plasticizers are chosen from the group consisting of butane triol 1,2,4 trinitrate, trimethylol ethane trinitrate, triethylene glycol dinitrate, bis (2,2 dinitropropyl) acetal and bis (2,2 dinitropropyl ) formal.
- the content by weight of plasticizer will generally be between 70 and 80% by weight relative to the weight of glycidyl polyazide used.
- the weight content of the energy binder / plasticizer assembly is advantageously between 30 and 40% by weight relative to the total weight of the composition.
- the composition contains an oxidizing charge which is constituted for at least 85% of its weight by ammonium nitrate.
- the whole of the oxidizing charge can consist of ammonium nitrate but it is essential within the framework of the present invention that the ammonium nitrate represents, by weight, at least 85% of the oxidizing charge.
- a stabilized ammonium nitrate will be used.
- the stabilizer may for example consist of a small amount of nickel oxide NiO.
- This quality of ammonium nitrate is sold commercially and generally contains 3% by weight of nickel oxide relative to pure ammonium nitrate.
- the expression "ammonium nitrate” covers the assembly constituted by pure ammonium nitrate and by the stabilizer possibly present.
- nickel oxide is noncombustible, its presence in small quantities proves to be not a problem in the context of the present invention.
- the oxidizing charge is not 100% made up of ammonium nitrate, it can be supplemented by triaminoguanidinium nitrate, by nitroguanidine or by a nitramine such as hexogen or octogen.
- the compositions preferred in the context of the present invention contain, as oxidizing charge, exclusively ammonium nitrate.
- a composition according to the invention may contain additives intended essentially to improve the combustion characteristics and in particular the plateau effect, that is to say the slight influence of the pressure on the combustion rate.
- the additives falling within the scope of the present invention exclude metals or metal compounds and are preferably chosen from the group consisting of potassium perchlorate, carbon black and m-methyl p-nitroaniline.
- the content by weight of additives can represent up to 3% by weight relative to the total weight of the composition.
- the weight content of the whole oxidizing charge / additives is advantageously between 70% and 60% by weight relative to the total weight of the composition.
- compositions according to the invention are advantageously carried out in the following manner.
- the basic constituents of the binder namely the glycidyl polyazide, the isocyanate, the energy plasticizer, the hardener and catalysts intended to promote the reaction of the isocyanate on the glycidyl polyazide, such as dibutyl dilaurate, are introduced into a mixer. tin or iron acetyl acetonate.
- the solid constituents namely the possibly stabilized oxidizing charge and, if appropriate, the additives are mixed.
- the mixture of solid constituents is added in successive fractions until a homogeneous paste is obtained which is put into final form by casting, injection or extrusion followed by baking to complete the crosslinking of the binder.
- compositions used in the context of the invention are generally in the form of pellets or else of solid or tubular blocks.
- compositions burn with combustion rates compatible with the requirements of automotive safety, and without producing solid residues. They also have the double advantage of having on the one hand a substantially constant combustion speed between 100 and 500 bars, that is to say between 10 and 50 MPa, and on the other hand providing combustion gases containing much less carbon monoxide than a traditional nitrocellulose-based composition.
- these compositions can advantageously be used in pyrotechnic gas generators intended for devices for protecting the occupants of a motor vehicle by airbags.
- these compositions also produce hot gases, they find their preferred application in pyrotechnic hot gas generators having only one ignition chamber and one combustion chamber directly connected to an airbag operating in addition to a belt. of security.
- composition was made: - Glycidyl polyazide (mass 2000) - 1,2,4 butane trinitrate triol - trimethylol ethane trinitrate 34 parts by weight - trimer biuret of hexamethylene diisocyanate. - Ammonium nitrate (NiO 3%) 65 parts by weight - m-methyl p-nitroaniline 0.5 parts by weight - diphenylamine 0.5 parts by weight
- the analysis of the combustion gases was as follows: nitrogen 30.6% by weight carbon monoxide 8.2% by weight carbon dioxide 22.6% by weight nitrogen oxides 0.1% by weight hydrogen 0.4% by weight various 0.9% by weight water 37.2% by weight
- This composition gave the following combustion rates: 18 mm / s at 20 Mpa 20 mm / s at 24 MPa 24 mm / s at 36 MPa 26 mm / s at 40 MPa
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Molecular Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Air Bags (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
La présente invention se rapporte au domaine de la sécurité automobile. Plus précisément l'invention concerne la protection, en cas de collision, des occupants d'un véhicule automobile au moyen d'un sac qui est gonflé par des gaz provenant de la combustion d'une composition pyrotechnique. L'invention est relative à une composition génératrice de gaz chauds non toxiques principalement constituée par un oxydant minéral et par un liant à base de polyazoture de glycidyle.The present invention relates to the field of automobile safety. More specifically, the invention relates to the protection, in the event of a collision, of the occupants of a motor vehicle by means of a bag which is inflated by gases originating from the combustion of a pyrotechnic composition. The invention relates to a composition generating non-toxic hot gases mainly consisting of an inorganic oxidant and a binder based on poly (glycidyl azide).
Il est connu de chercher à assurer la sécurité des occupants d'un véhicule automobile en les protégeant contre les chocs en cas de collision grâce à des sacs gonflés par des gaz provenant de la combustion d'une composition pyrotechnique. Les gaz gonflant les dits sacs doivent répondre à de nombreux impératifs:
- ils doivent répondre à des normes très sévères au plan de la toxicité,
- ils doivent être produits en des temps très courts, de l'ordre de quelques dizaines de millisecondes,
- ils ne doivent pas contenir des particules solides susceptibles de constituer des points chauds à l'intérieur du sac.
- they must meet very strict standards in terms of toxicity,
- they must be produced in very short times, of the order of a few tens of milliseconds,
- they must not contain solid particles likely to constitute hot spots inside the bag.
Pour des raisons évidentes de sécurité vis à vis des risques d'incendie, les compositions pyrotechniques générant principalement, par combustion, de l'azote sont préférées. Ces compositions sont en général constituées par un azoture alcalin ou alcalino-terreux et par un oxydant. De telles compositions sont, par exemple, décrites dans les brevets US 3741585, 4203787 ou 4547235. Ces compositions génèrent des gaz dits "froids" dont la température en sortie de chambre de combustion se situe en général entre 600°C et 800°C mais qui contiennent des résidus solides qu'il convient de filtrer avant l'entrée des gaz dans le sac. De telles compositions nécessitent la mise en oeuvre de générateurs complexes, comprenant une ou plusieurs chambres de filtration et de refroidissement. Par ailleurs ces compositions ont une tenue mécanique médiocre. Afin de remédier à ce dernier inconvénient il a alors été proposé d'utiliser dans ces compositions un liant constitué par le produit de réaction d'un polyazoture de glycidyle avec un polyisocyanate, comme décrit par exemple dans le brevet US 4976795. Ce type de composition présente une meilleure tenue mécanique mais nécessite cependant des générateurs possédant une chambre de filtration.For obvious safety reasons with regard to fire risks, pyrotechnic compositions mainly generating, by combustion, nitrogen are favorite. These compositions generally consist of an alkali or alkaline earth azide and an oxidant. Such compositions are, for example, described in US Patents 3741585, 4203787 or 4547235. These compositions generate so-called "cold" gases whose temperature at the outlet of the combustion chamber is generally between 600 ° C and 800 ° C but which contain solid residues which must be filtered before the gases enter the bag. Such compositions require the use of complex generators, comprising one or more filtration and cooling chambers. Furthermore, these compositions have poor mechanical strength. In order to remedy this last drawback, it has then been proposed to use in these compositions a binder consisting of the reaction product of a glycidyl polyazide with a polyisocyanate, as described for example in US Pat. No. 4,976,795. This type of composition has better mechanical strength but however requires generators having a filtration chamber.
Depuis ces dernières années un autre type de dispositif a été développé selon lequel le sac de protection est gonflé par une petite quantité de gaz chauds, ayant une température plus élevée que dans la solution précédente. Cette petite quantité de gaz chauds est suffisante pour assurer le déploiement rapide du sac tout en représentant une quantité minime de matière dont le refroidissement est assuré par la chute rapide de pression lors du déploiement du sac. Ce type de solution est particulièrement intéressant dans les dispositifs de protection faisant appel à des sacs de faible volume fonctionnant en complément d'une ceinture de sécurité comme illustré par exemple dans la demande de brevet PCT WO 90/05651 ou dans la demande de brevet FR 2652322. Dans ce type de solution on utilise le plus souvent comme composition pyrotechnique des compositions à base de nitrocellulose, éventuellement plastifiée par de la nitroglycérine, qui présentent l'avantage de ne générer aucun résidu solide et de permettre l'emploi de générateurs très simples constitués essentiellement par un inflammateur et une chambre de combustion sans aucune chambre de filtration. Néanmoins ces compositions à base de nitrocellulose présentent d'autres inconvénients. Les gaz de combustion de ces compositions présentent une teneur relativement élevée en produits toxiques, notamment en monoxyde de carbone, ce qui fait que certains constructeurs de véhicules automobiles hésitent à utiliser des dispositifs de protection faisant appel à ces compositions. Par ailleurs la vitesse de combustion de ces compositions dépend beaucoup de la pression régnant dans la chambre de combustion, la courbe représentant la vitesse de combustion d'une telle composition en fonction de la pression ne présentant pas de "plateau" dans la zone de fonctionnement. Il s'agit là d'un inconvénient majeur car dans les dispositifs de protection du type de ceux décrits dans les brevets WO 90/05651 et FR 2652322, au moment du déploiement brutal du sac, il se produit dans la chambre de combustion qui lui est directement reliée, une chute brutale de pression. Cette chute de pression provoque avec les compositions à base de nitrocellulose au moins une baisse sensible de leur vitesse de combustion qui n'est en elle-même déjà pas souhaitable quand elle n'entraîne pas une extinction pure et simple de la composition. Enfin les compositions pyrotechniques de ce type présentent des problèmes de vieillissement dans la mesure où la stabilité des composés nitrés se dégrade dans le temps. Or les dispositifs de protection placés dans les véhicules automobiles doivent pouvoir conserver une fiabilité totale de fonctionnement pendant de nombreuses années.In recent years another type of device has been developed in which the protective bag is inflated by a small amount of hot gas, having a higher temperature than in the previous solution. This small amount of hot gas is sufficient to ensure rapid deployment of the bag while representing a minimal amount of material whose cooling is ensured by the rapid drop in pressure during deployment of the bag. This type of solution is particularly advantageous in protective devices using small volume bags operating in addition to a safety belt as illustrated for example in the patent application. PCT WO 90/05651 or in patent application FR 2652322. In this type of solution is most often used as pyrotechnic composition compositions based on nitrocellulose, optionally plasticized with nitroglycerin, which have the advantage of generating no solid residue and allow the use of very simple generators consisting essentially of an igniter and a combustion chamber without any filtration chamber. However, these nitrocellulose-based compositions have other drawbacks. The combustion gases of these compositions have a relatively high content of toxic products, in particular carbon monoxide, which means that certain motor vehicle manufacturers are reluctant to use protective devices using these compositions. Furthermore, the combustion speed of these compositions very much depends on the pressure prevailing in the combustion chamber, the curve representing the combustion speed of such a composition as a function of the pressure having no "plateau" in the operating zone. . This is a major drawback because in protection devices of the type described in patents WO 90/05651 and FR 2652322, when the bag suddenly deploys, it occurs in the combustion chamber which is directly connected, a sudden drop in pressure. This pressure drop causes, with the nitrocellulose-based compositions, at least a significant drop in their combustion rate which is in itself already undesirable when it does not result in outright extinction of the composition. Finally, pyrotechnic compositions of this type present aging problems insofar as the stability of the nitro compounds degrades over time. The protective devices placed in motor vehicles must be able to maintain full operational reliability for many years.
Les compositions pyrotechniques composites comprenant essentiellement un oxydant entièrement combustible et un liant organique qui sont connues et utilisées dans le domaine de la propulsion des fusées, présentent une bonne résistance au vieillissement et une vitesse de combustion souvent peu dépendante de la pression. Malheureusement les compositions de ce type connues à ce jour ne sont pas utilisables dans les dispositifs de sécurité automobile mentionnés précèdement en raison de la toxicité de leurs gaz de combustion ou de la présence, dans ces derniers, de résidus solides chauds.Composite pyrotechnic compositions essentially comprising a fully combustible oxidant and an organic binder which are known and used in the field of rocket propulsion have good resistance to aging and a combustion rate which is often not very dependent on pressure. Unfortunately, the compositions of this type known to date cannot be used in the automobile safety devices mentioned above due to the toxicity of their combustion gases or the presence, in the latter, of hot solid residues.
Ainsi le brevet US 5 074 938 décrit des propergols pour l'autopropulsion constitués principalement par un liant du type polyadipate de glycol, par un plastifiant énergétique de ce liant, par du nitrate d'ammonium et par des particules de bore. Une telle composition présente bien un effet "plateau" avec une courbe de la vitesse de combustion en fonction de la pression qui révèle un faible exposant de pression, mais les gaz générés sont, de par la nature même du liant, riches en monoxyde de carbone et par ailleurs ils contiennent des particules solides de bore. De tels gaz ne peuvent pas être utilisés, sans dispositif de filtration, pour gonfler un coussin de sécurité pour véhicule automobile.Thus, US Pat. No. 5,074,938 describes propellants for self-propulsion constituted mainly by a binder of the polyadipate glycol type, by an energy plasticizer of this binder, by ammonium nitrate and by boron particles. Such a composition does indeed have a "plateau" effect with a curve of the combustion rate as a function of the pressure which reveals a low pressure exponent, but the gases generated are, by the very nature of the binder, rich in carbon monoxide and moreover they contain solid particles of boron. Such gases cannot be used, without a filtration device, to inflate a safety cushion for a motor vehicle.
Le brevet US 4938813 illustre un autre type de telles compositions qui sont principalement constituées par un liant à base de polyazoture de glycidyle et par une charge oxydante qui est une nitramine comme l'hexogène ou l'octogène. Les compositions de ce type présentent bien un effet "plateau" avec une vitesse de combustion relativement peu dépendante de la pression, mais la présence de nitramines entraîne une toxicité élevée des gaz de combustion incompatible avec les normes exigées pour la sécurité automobile. Par ailleurs ces compositions contiennent souvent comme additifs des sels de plombs qui génèrent des résidus solides. La demande WO 89/03372 décrit des compositions analogues contenant un métal comme l'aluminium et un composé organique polymérisé "neutre" assurant une meilleure cohésion des charges.US Pat. No. 4,938,813 illustrates another type of such compositions which are mainly constituted by a binder based on glycidyl polyazide and by an oxidizing charge which is a nitramine such as hexogen or octogen. Compositions of this type have although a "plateau" effect with a combustion speed relatively little dependent on the pressure, but the presence of nitramines leads to a high toxicity of the combustion gases incompatible with the standards required for automobile safety. Furthermore, these compositions often contain lead additives which generate solid residues as additives. Application WO 89/03372 describes similar compositions containing a metal such as aluminum and a “neutral” polymerized organic compound ensuring better cohesion of the charges.
Un autre type de compositions est illustré dans les demandes de brevets japonais 62265192 et 63248791. Ces compositions sont principalement constituées par un liant à base d'un copolymère de polyazoture de glycidyle et de polyépoxyde et par une charge minérale qui est soit du nitrate d'ammonium, soit du perchlorate d'ammonium. Ces compositions ne présentent pas d'effet plateau marqué et par ailleurs la présence de motifs polyépoxyde dans le liant entraîne une teneur importante dans les gaz de combustion de produits toxiques, notamment de monoxyde de carbone.Another type of composition is illustrated in Japanese patent applications 62265192 and 63248791. These compositions are mainly constituted by a binder based on a copolymer of polyazide of glycidyl and polyepoxide and by a mineral filler which is either nitrate of ammonium, or ammonium perchlorate. These compositions do not have a marked plateau effect and, moreover, the presence of polyepoxide units in the binder results in a significant content in the combustion gases of toxic products, in particular carbon monoxide.
L'homme de métier est donc à la recherche de compositions pyrotechniques générant par combustion des gaz chauds qui soient peu toxiques, dont la vitesse de combustion soit peu dépendante de la pression dans le domaine d'utilisation qui se situe habituellement entre 100 et 500 bars, c'est à dire entre 10 et 50 MPa (Méga Pascal), et enfin qui brûlent sans résidus solides. Le but de la présente invention est de proposer à l'homme de métier des compositions pyrotechniques génératrices de gaz chauds qui satisfont aux exigences exposées ci-dessus sans présenter les inconvénients qui viennent d'être mentionnés.Those skilled in the art are therefore looking for pyrotechnic compositions generating by combustion hot gases which are not very toxic, the combustion rate of which is not very dependent on the pressure in the field of use which is usually between 100 and 500 bars. , that is to say between 10 and 50 MPa (Méga Pascal), and finally which burn without solid residues. The object of the present invention is to provide a person skilled in the art with pyrotechnic compositions which generate hot gases which meet the requirements set out above without having the drawbacks which arise. to be mentioned.
L'invention propose donc l'utilisation, comme composition pyrotechnique dans un dispositif de protection des occupants d'un véhicule automobile au moyen de sacs gonflés par des gaz provenant de la combustion d'une composition pyrotechnique, d'une composition comprenant notamment :
- un liant organique porteur de groupes azotures qui est constitué par le produit de réaction d'un polyazoture de glycidyle à terminaisons hydroxyles avec au moins un polyisocyanate,
- un plastifiant énergétique,
- une charge oxydante constituée à raison d'au moins 85% de son poids par du nitrate d'ammonium.
- an organic binder carrying azide groups which is constituted by the reaction product of a glycidyl polyazide with hydroxyl endings with at least one polyisocyanate,
- an energy plasticizer,
- an oxidizing charge consisting of at least 85% of its weight by ammonium nitrate.
Selon une première réalisation préférée de l'invention les compositions contiennent au moins un additif choisi dans le groupe constitué par le perchlorate d'ammonium, le noir de carbone et la m-méthyl p-nitro aniline.According to a first preferred embodiment of the invention, the compositions contain at least one additive chosen from the group consisting of ammonium perchlorate, carbon black and m-methyl p-nitro aniline.
Avantageusement la teneur pondérale en additif représente jusqu'à 3% en poids du poids total de la composition, la teneur pondérale de l'ensemble liant/plastifiant énergétique étant comprise entre 30 et 40% en poids du poids total de la composition tandis que la teneur pondérale de l'ensemble charge oxydante/additifs est comprise entre 70% et 60% en poids du poids total de la composition.Advantageously, the weight content of additive represents up to 3% by weight of the total weight of the composition, the weight content of the energy binder / plasticizer assembly being between 30 and 40% by weight of the total weight of the composition while the weight content of the whole oxidizing charge / additives is between 70% and 60% by weight of the total weight of the composition.
Selon une seconde réalisation préférée de l'invention le dit plastifiant énergétique est choisi dans le groupe constitué par le 1,2,4 trinitrate de butane triol, le trinitrate de triméthyloléthane, le dinitrate de triéthylène glycol, le bis (2,2 dinitropropyl) acétal, le bis (2,2 dinitropropyl) formal.According to a second preferred embodiment of the invention, the said energy plasticizer is chosen from the group consisting of butane triol 1,2,4 trinitrate, trimethylolethane trinitrate, triethylene glycol dinitrate, bis (2,2 dinitropropyl) acetal, bis (2,2 dinitropropyl) formal.
La teneur pondérale en plastifiant est comprise entre 70% et 80% en poids par rapport au poids du polyazoture de glycidyle utilisé.
Les compositions utilisables dans le cadre de l'invention se caractérisent essentiellement ;
- par l'emploi exclusif de polyazoture de glycidyle comme polymère hydroxylé constitutif du liant, les copolymères obtenus à partir de l'azoture de glycidyle et d'un mononère hydroxylé n'entrant pas dans le cadre de la présente invention,
- par l'absence dans la composition de composés métalliques tels que l'aluminium ou le bore,
- par l'emploi du nitrate d'ammonium comme constituant principal de la charge oxydante.
The compositions which can be used in the context of the invention are essentially characterized;
- by the exclusive use of glycidyl polyazide as the hydroxylated polymer constituting the binder, the copolymers obtained from glycidyl azide and a hydroxylated mononer not falling within the scope of the present invention,
- by the absence in the composition of metallic compounds such as aluminum or boron,
- by the use of ammonium nitrate as the main constituent of the oxidizing charge.
Dans ces conditions les compositions ainsi définies brûlent en dégageant essentiellement de l'azote sans produire de résidus solides. De surcroît il a été observé, et ce malgré l'absence de composés métalliques, que ces compositions ont des vitesses de combustion peu dépendantes de la pression entre 150 et 500 bars soit entre 15 et 50 MPa (Méga Pascal) et d'une valeur compatible avec les exigences de la sécurité automobile. Ces compositions se révèlent donc particulièrement bien adaptées pour des générateurs pyrotechniques de gaz destinés à gonfler, en cas d'accident de véhicules automobiles, des coussins de protection, et notamment elles conviennent bien aux générateurs sans dispositif de filtration qui sont très exposés à la chute brutale de pression occasionnée par le déploiement subit du coussin gonfable.Under these conditions, the compositions thus defined burn, essentially giving off nitrogen without producing solid residues. In addition, it has been observed, and this despite the absence of metallic compounds, that these compositions have combustion rates that are not very dependent on pressure between 150 and 500 bars, ie between 15 and 50 MPa (Mega Pascal) and of a value compatible with the requirements of automotive safety. These compositions therefore prove to be particularly well suited for pyrotechnic gas generators intended to inflate, in the event of a motor vehicle accident, protective cushions, and in particular they are well suited to generators without a filtration device which are very exposed to falling. sudden pressure caused by the sudden deployment of the airbag.
Il est donné ci-après une description détaillée de la mise en oeuvre préférée de l'invention.A detailed description of the preferred implementation of the invention is given below.
Une composition utilisable dans le cadre de l'invention comprend essentiel- lement, comme il a été indiqué plus haut, un liant, un plastifiant énergétique, une charge oxydante et éventuellement des additifs.A composition which can be used in the context of the invention essentially comprises, as indicated above, a binder, an energetic plasticizer, an oxidizing charge and optionally additives.
Selon une première caractéristique essentielle de l'invention le liant est constitué par le produit de réaction d'un polyazoture de glycidyle à terminaisons hydroxyles OH avec au moins un polyisoyanate.According to a first essential characteristic of the invention, the binder consists of the reaction product of a glycidyl polyazide with OH hydroxyl endings with at least one polyisoyanate.
Les polyazotures de glycidyle à terminaisons hydroxyles OH utilisables dans le cadre de la présente invention sont des polyéthers de formule générale :
Ces polymères sont en général obtenus par réaction de l'azoture de sodium sur une polyépichlorhydrine comme décrit par exemple dans les brevets US 4 268 450, 4 379 894 ou 4 486 351. On utilisera en général des polyazotures de glycidyle dont la masse moléculaire est comprise entre 600 et 7000 et on préfèrera ceux dont la masse moléculaire est comprise entre 1500 et 2500.These polymers are generally obtained by reaction of sodium azide on a polyepichlorohydrin as described for example in US Patents 4,268,450, 4,379,894 or 4,486,351. In general, glycidyl polyazides with a molecular weight will be used between 600 and 7000 and we prefer those whose molecular mass is between 1500 and 2500.
Comme polyisocyanate on peut utiliser les diisocyanates et triisocyanates aliphatiques, cycloaliphatiques ou aromatiques usuels comme par exemple le méthyl-1 cyclohexane-2,4 diisocyanate, le méthyl-1 cyclohexane-2,6 diisocyanate, le dicyclohexylmethane-4,4' diisocyanate, l'isophorone diisocyanate , le méthylène diisocyanate, l'hexane-1,6 diisocyanate, le triméthyl-2 ,2,4 hexane-1,6 diisocyanate, le toluène diisocyanate, le biuret trimère de l'hexaméthylène diisocyanate, le polyméthylène polyphényl isocyanate.As polyisocyanate, aliphatic, cycloaliphatic or usual aromatics such as, for example, methyl-1 cyclohexane-2,4 diisocyanate, methyl-1 cyclohexane-2,6 diisocyanate, dicyclohexylmethane-4,4 'diisocyanate, isophorone diisocyanate, methylene diisocyanate, hexane-1 , 6 diisocyanate, trimethyl-2, 2,4 hexane-1,6 diisocyanate, toluene diisocyanate, the biuret trimer of hexamethylene diisocyanate, polymethylene polyphenyl isocyanate.
Cependant on préfèrera comme polyisocyanate le biuret trimère de l'hexaméthylène diisocyanate de formule :
et les polyméthylène polyphénylisocyanates de formule :
dans laquelle x représente un nombre entier ou nul et qui ont une fonctionnalité moyenne en groupe NCO de 2,7.However, the trimer biuret of hexamethylene diisocyanate of formula: polyisocyanate is preferred:
and polymethylene polyphenylisocyanates of formula:
in which x represents an integer or zero and which have an average NCO group functionality of 2.7.
Dans la formulation du liant selon l'invention le rapport NCO : OH est voisin de 1 : 1.In the formulation of the binder according to the invention, the NCO: OH ratio is close to 1: 1.
Afin d'améliorer la réticulation tridimensionnelle du liant on pourra rajouter à l'isocyanate un peu d'un triol court comme par exemple le triméthylolpropane.In order to improve the three-dimensional crosslinking of the binder, it is possible to add to the isocyanate a little of a short triol such as, for example, trimethylolpropane.
Selon une seconde caractéristique essentielle de l'invention la composition contient un plastifiant énergétique du liant. Les plastifiants préférés sont choisis dans le groupe constitué par le 1,2,4 trinitrate de butane triol, le trinitrate de triméthylol éthane, le dinitrate de triéthylène glycol, le bis (2,2 dinitropropyl) acétal et le bis (2,2 dinitropropyl) formal.According to a second essential characteristic of the invention, the composition contains an energetic plasticizer for the binder. The preferred plasticizers are chosen from the group consisting of butane triol 1,2,4 trinitrate, trimethylol ethane trinitrate, triethylene glycol dinitrate, bis (2,2 dinitropropyl) acetal and bis (2,2 dinitropropyl ) formal.
La teneur pondérale en plastifiant sera en général comprise entre 70 et 80% en poids par rapport au poids de polyazoture de glycidyle utilisé.The content by weight of plasticizer will generally be between 70 and 80% by weight relative to the weight of glycidyl polyazide used.
Par ailleurs la teneur pondérale de l'ensemble liant/plastifiant énergétique est avantageusement comprise entre 30 et 40% en poids par rapport au poids total de la composition.Furthermore, the weight content of the energy binder / plasticizer assembly is advantageously between 30 and 40% by weight relative to the total weight of the composition.
Selon une troisième caractéristique essentielle de l'invention la composition contient une charge oxydante qui est constituée pour at moins 85% de son poids par du nitrate d'ammonium.According to a third essential characteristic of the invention, the composition contains an oxidizing charge which is constituted for at least 85% of its weight by ammonium nitrate.
La totalité de la charge oxydante peut être constituée par du nitrate d'ammonium mais il est essentiel dans le cadre de la présente invention que le nitrate d'ammonium représente, en poids, au moins 85% de la charge oxydante.The whole of the oxidizing charge can consist of ammonium nitrate but it is essential within the framework of the present invention that the ammonium nitrate represents, by weight, at least 85% of the oxidizing charge.
On utilisera avantageusement un nitrate d'ammonium stabilisé. Le stabilisant pourra par exemple être constitué par un peu d'oxyde de nickel NiO. Cette qualité de nitrate d'ammonium est vendue dans le commerce et contient en général 3% en poids d'oxyde de nickel par rapport au nitrate d'ammonium pur. Dans la présente description l'expression "nitrate d'ammonium" recouvre l'ensemble constituée par le nitrate d'ammonium pur et par le stabilisant éventuellement présent. Bien que l'oxyde de nickel soit non combustible, sa présence en faible quantité s'avère non gênante dans le cadre de la présente invention.Advantageously, a stabilized ammonium nitrate will be used. The stabilizer may for example consist of a small amount of nickel oxide NiO. This quality of ammonium nitrate is sold commercially and generally contains 3% by weight of nickel oxide relative to pure ammonium nitrate. In the present description the expression "ammonium nitrate" covers the assembly constituted by pure ammonium nitrate and by the stabilizer possibly present. Although nickel oxide is noncombustible, its presence in small quantities proves to be not a problem in the context of the present invention.
Lorsque la charge oxydante n'est pas constituée à 100% par du nitrate d'ammonium, elle peut être completée par du nitrate de triaminoguanidinium, par de la nitroguanidine ou encore par une nitramine comme l'hexogène ou l'octogène. Toutefois les compositions préférées dans le cadre de la présente invention contiennent comme charge oxydante exclusivement du nitrate d'ammonium.
Enfin une composition selon l'invention peut contenir des additifs destinés essentiellemnt à améliorer les caractéristiques de combustion et notamment l'effet plateau c'est-à-dire la faible influence de la pression sur la vitesse de combustion.
Les additifs entrant dans le cadre de la présente invention excluent les métaux ou les composés métalliques et sont préférentiellement choisis dans le groupe constitué par le perchlorate de potassium, le noir de carbone et la m-méthyl p-nitroaniline.
La teneur pondérale en additifs peut représenter jusqu'à 3% en poids par rapport au poids total de la composition. Par ailleurs la teneur pondérale de l'ensemble charge oxydante/additifs est avantageusement comprise entre 70% et 60% en poids par rapport au poids total de la composition.When the oxidizing charge is not 100% made up of ammonium nitrate, it can be supplemented by triaminoguanidinium nitrate, by nitroguanidine or by a nitramine such as hexogen or octogen. However, the compositions preferred in the context of the present invention contain, as oxidizing charge, exclusively ammonium nitrate.
Finally, a composition according to the invention may contain additives intended essentially to improve the combustion characteristics and in particular the plateau effect, that is to say the slight influence of the pressure on the combustion rate.
The additives falling within the scope of the present invention exclude metals or metal compounds and are preferably chosen from the group consisting of potassium perchlorate, carbon black and m-methyl p-nitroaniline.
The content by weight of additives can represent up to 3% by weight relative to the total weight of the composition. Furthermore, the weight content of the whole oxidizing charge / additives is advantageously between 70% and 60% by weight relative to the total weight of the composition.
La formulation des compositions selon l'invention est avantageusement effectuée de la manière suivante.The formulation of the compositions according to the invention is advantageously carried out in the following manner.
Dans un malaxeur on introduit les constituants de base du liant à savoir le polyazoture de glycidyle, l'isocyanate, le plastifiant énergétique, le durcisseur et des catalyseurs destinés à favoriser la réaction de l'isocyanate sur le polyazoture de glycidyle comme le dilaurate de dibutyl étain ou l'acétyl acétonate de fer. Dans un mélangeur à poudre, on mélange les constituants solides à savoir la charge oxydante éventuellement stabilisé et, le cas échéant, les additifs. Après mise en route du malaxeur on rajoute par fractions successives le mélange des constituants solides jusqu'à obtention d'une pâte homogène qui est mise sous forme définitive par coulée, injection ou extrusion suivie par une cuisson pour parachever la réticulation du liant.The basic constituents of the binder, namely the glycidyl polyazide, the isocyanate, the energy plasticizer, the hardener and catalysts intended to promote the reaction of the isocyanate on the glycidyl polyazide, such as dibutyl dilaurate, are introduced into a mixer. tin or iron acetyl acetonate. In a powder mixer, the solid constituents, namely the possibly stabilized oxidizing charge and, if appropriate, the additives are mixed. After starting the kneader, the mixture of solid constituents is added in successive fractions until a homogeneous paste is obtained which is put into final form by casting, injection or extrusion followed by baking to complete the crosslinking of the binder.
Les compositions utilisées dans le cadre l'invention se présentent en général sous forme de pastilles ou encore de blocs pleins ou tubulaires.The compositions used in the context of the invention are generally in the form of pellets or else of solid or tubular blocks.
Ces compositions brûlent avec des vitesses de combustion compatibles avec les exigences de la sécurité automobile, et sans produire de résidus solides. Elles présentent par ailleurs le double avantage d'avoir d'une part une vitesse de combustion sensiblement constante entre 100 et 500 bars c'est à dire entre 10 et 50 MPa et de fournir d'autre part des gaz de combustion contenant beaucoup moins de monoxyde de carbone qu'une composition traditionnelle à base de nitrocellulose.These compositions burn with combustion rates compatible with the requirements of automotive safety, and without producing solid residues. They also have the double advantage of having on the one hand a substantially constant combustion speed between 100 and 500 bars, that is to say between 10 and 50 MPa, and on the other hand providing combustion gases containing much less carbon monoxide than a traditional nitrocellulose-based composition.
On constate par ailleurs que les gaz de combustion de ces compositions ne contiennent pratiquement pas d'oxydes d'azote et ce malgré une forte proportion de constituants azotés dans la composition.It is also found that the combustion gases of these compositions contain practically no nitrogen oxides, despite a high proportion of nitrogenous constituents in the composition.
En raison de cet ensemble de propriétés ces compositions peuvent avantageusement être utilisées dans les générateurs pyrotechniques de gaz destinés aux dispositifs de protection par coussins gonflables des occupants d'un véhicule automobile. Comme ces compositions produisent par ailleurs des gaz chauds elles trouvent leur application préférentielle dans les générateurs pyrotechniques de gaz chauds ne comportant qu'une chambre d'allumage et qu'une chambre de combustion reliée directement à un coussin gonflable fonctionnant en complément d'une ceinture de sécurité.Due to this set of properties, these compositions can advantageously be used in pyrotechnic gas generators intended for devices for protecting the occupants of a motor vehicle by airbags. As these compositions also produce hot gases, they find their preferred application in pyrotechnic hot gas generators having only one ignition chamber and one combustion chamber directly connected to an airbag operating in addition to a belt. of security.
Les exemples qui suivent illustrent, à titre non limitatif, certaines possibilités de mise en oeuvre de l'invention.The examples which follow illustrate, without limitation, certain possibilities of implementing the invention.
On a fabriqué la composition suivante :
Cette composition a donné les vitesses de combustion suivantes :
29 mm/s à 32 MPa
30 mm/s à 36 MPa
31 mm/s à 40 MPa
32 mm/s à 44 MPaThis composition gave the following combustion rates:
29 mm / s at 32 MPa
30 mm / s at 36 MPa
31 mm / s at 40 MPa
32 mm / s at 44 MPa
L'analyse des gaz de combustion a été la suivante :
On a fabriqué la composition suivante
Cette composition a donné les vitesses de combustion suivantes :
18 mm/s à 20 Mpa
20 mm/s à 24 MPa
24 mm/s à 36 MPa
26 mm/s à 40 MPaThis composition gave the following combustion rates:
18 mm / s at 20 Mpa
20 mm / s at 24 MPa
24 mm / s at 36 MPa
26 mm / s at 40 MPa
L'analyse des gaz de combustion a été la suivante :
Claims (6)
- Use, as pyrotechnic composition in a device for protecting the occupants of a motor vehicle by means of bags which are inflated by gases originating from the combustion of a pyrotechnic composition, of a composition comprising especially:- an organic binder bearing azide groups, which consists of the product of reaction of a polyglycidyl aside containing hydroxyl ends with at least one polyisocyanate,- an energetic plasticizer,- an oxidizing filler at least 85 % of the weight of which consists of ammonium nitrate.
- Use according to Claim 1, characterized in that the said composition contains at least one additive chosen from the group consisting of ammonium perchlorate, carbon black and m-methyl-p-nitroaniline.
- Use according to Claim 2, characterized in that the weight content of additive represents up to 3 % by weight of the total weight of the composition.
- Use according to Claim 3, characterized in that the weight content of the combination of binder/energetic plasticizer is between 30 % and 40 % by weight of the total weight of the composition and in that the weight content of the combination of oxidizing filler/additives is between 70 % and 60 % by weight of the total weight of the composition.
- Use according to Claim 4, characterized in that the said energetic plasticizer is chosen from the group consisting of 1,2,4-butanetriol trinitrate, trimethylolethane trinitrate, triethylene glycol dinitrate, bis(2,2-dinitropropyl)acetal and bis(2,2-dinitropropyl)formal.
- Use according to Claim 5, characterized in that the weight content of plasticizer is between 70 % and 80 % by weight relative to the weight of the polyglycidyl azide employed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9207067A FR2692257B1 (en) | 1992-06-12 | 1992-06-12 | Pyrotechnic composition generating non-toxic hot gases and its use in a device for protecting the occupants of a motor vehicle. |
| FR9207067 | 1992-06-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0576326A1 EP0576326A1 (en) | 1993-12-29 |
| EP0576326B1 true EP0576326B1 (en) | 1996-11-06 |
Family
ID=9430641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93401513A Expired - Lifetime EP0576326B1 (en) | 1992-06-12 | 1993-06-14 | Pyrotechnic composition, which generates a hot non-toxic gas and use thereof in a protection system for motor vehicle occupants |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0576326B1 (en) |
| JP (1) | JPH0669916B2 (en) |
| DE (1) | DE69305793T2 (en) |
| FR (1) | FR2692257B1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4109317B2 (en) * | 1994-01-19 | 2008-07-02 | アライアント・テクシステムズ・インコーポレーテッド | Metal complexes used as gas generating agents |
| DE4435524C2 (en) * | 1994-10-05 | 1996-08-22 | Fraunhofer Ges Forschung | Solid fuel based on pure or phase-stabilized ammonium nitrate |
| DE4435523C1 (en) * | 1994-10-05 | 1996-06-05 | Fraunhofer Ges Forschung | Solid fuel based on phase-stabilized ammonium nitrate |
| GB2296248A (en) * | 1994-12-22 | 1996-06-26 | Secr Defence | Inert and energetic prepolymers co-cured with isocyanate |
| US5641938A (en) * | 1995-03-03 | 1997-06-24 | Primex Technologies, Inc. | Thermally stable gas generating composition |
| US5868424A (en) * | 1996-03-06 | 1999-02-09 | Oea, Inc. | Substantially smoke-free and particulate-free inflator for inflatable safety restraint system |
| JP3641343B2 (en) * | 1997-03-21 | 2005-04-20 | ダイセル化学工業株式会社 | Gas generator composition for low residue airbag |
| JP3608902B2 (en) | 1997-03-24 | 2005-01-12 | ダイセル化学工業株式会社 | Gas generating agent composition and molded body thereof |
| US6143103A (en) * | 1998-01-27 | 2000-11-07 | Trw Inc. | Gas generating material for vehicle occupant protection device |
| DE19821010C1 (en) * | 1998-05-11 | 1999-10-28 | Bayern Chemie Gmbh Flugchemie | Gas generator solid propellant for submarine emergency surfacing system |
| DE69834107T2 (en) * | 1998-07-13 | 2006-09-21 | Nof Corp. | Gas Generating Compositions |
| US6334917B1 (en) | 1998-10-23 | 2002-01-01 | Autoliv Asp, Inc. | Propellant compositions for gas generating apparatus |
| US6176517B1 (en) | 1998-10-23 | 2001-01-23 | Autoliv Aspinc. | Gas generating apparatus |
| US6120626A (en) * | 1998-10-23 | 2000-09-19 | Autoliv Asp Inc. | Dispensing fibrous cellulose material |
| JP4207425B2 (en) | 1999-10-06 | 2009-01-14 | 日油株式会社 | Gas generant composition |
| DE102008048340B3 (en) * | 2008-09-22 | 2010-01-14 | Autoliv Development Ab | Two-layer airbag blowing up device for security system of motor vehicle, has inflator producing air flow that is directed from outer side of airbag, and opening combustible in layer of airbag |
| FR3088929B1 (en) * | 2018-11-26 | 2021-05-14 | Arianegroup Sas | Process for the preparation of composite pyrotechnics |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2224740B (en) * | 1985-08-30 | 1990-08-22 | Minnesota Mining & Mfg | Hydroxyl-terminated polyepichlorohydrin and derivatives |
| US4915755A (en) * | 1987-10-02 | 1990-04-10 | Kim Chung S | Filler reinforcement of polyurethane binder using a neutral polymeric bonding agent |
| US5074938A (en) * | 1990-05-25 | 1991-12-24 | Thiokol Corporation | Low pressure exponent propellants containing boron |
| US5076868A (en) * | 1990-06-01 | 1991-12-31 | Thiokol Corporation | High performance, low cost solid propellant compositions producing halogen free exhaust |
-
1992
- 1992-06-12 FR FR9207067A patent/FR2692257B1/en not_active Expired - Fee Related
-
1993
- 1993-06-07 JP JP5135757A patent/JPH0669916B2/en not_active Expired - Fee Related
- 1993-06-14 DE DE69305793T patent/DE69305793T2/en not_active Expired - Fee Related
- 1993-06-14 EP EP93401513A patent/EP0576326B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| FR2692257A1 (en) | 1993-12-17 |
| JPH0692770A (en) | 1994-04-05 |
| FR2692257B1 (en) | 1995-05-05 |
| EP0576326A1 (en) | 1993-12-29 |
| DE69305793D1 (en) | 1996-12-12 |
| DE69305793T2 (en) | 1997-05-28 |
| JPH0669916B2 (en) | 1994-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0576326B1 (en) | Pyrotechnic composition, which generates a hot non-toxic gas and use thereof in a protection system for motor vehicle occupants | |
| EP1216977B1 (en) | Hydrocarbon binder containing pyrotechnic gas-generating compositions and method for continuous manufacturing | |
| US5507891A (en) | Propellant composition for automotive safety applications | |
| EP1037864B1 (en) | Pyrotechnic mixtures generating non-toxic gases based on ammonium perchlorate | |
| EP0659712B1 (en) | Pyrotechnic compositions for producing clean non-toxic gases containing an elastomeric thermoplastic binder | |
| EP2139828B1 (en) | Gas-generating pyrotechnic compound and production process. | |
| FR2714374A1 (en) | Solid pyrotechnic compositions with thermoplastic binder and silylferrocene polybutadiene plasticizer. | |
| EP0816307B1 (en) | Clean-gas generating pyrotechnic compositions and use thereof in a gas generator employed in a protection system in motor vehicles | |
| WO2005077862A2 (en) | Gas-generating pyrotechnical compositions and pyrotechnical compounds for automotive safety | |
| EP0404651B1 (en) | Solid gas-generating composition and its application in gas generators for inflatable safety bags in motor vehicles | |
| WO2007060365A2 (en) | Semi-continuous dual-component method for obtaining a polyurethane-matrix composite explosive charge | |
| EP0924177B1 (en) | Pyrotechnic composition for generating of a clean gas with a low nitrogen oxide content and pellets thereof | |
| EP0816306B1 (en) | Propellants with a high specific impulsion, containing furazane derivatives | |
| EP0930284B1 (en) | Ablative solid material for hybrid gas generator | |
| EP3515881B1 (en) | Composite pyrotechnic product containing an anti-gleam agent of potassium salt type | |
| FR2857359A1 (en) | GAS GENERATING PYROTECHNIC COMPOSITION FOR MOTOR VEHICLE SAFETY AND BURNING AT COMBUSTION TEMPERATURES LESS THAN 2200 K | |
| JPH07133180A (en) | Gas generant composition | |
| EP3687962B1 (en) | Gas-generating composition | |
| FR3139819A1 (en) | composite propellant with reduced burn rate | |
| FR3005657A1 (en) | NON-SMOKE PROPELLANT COMPOSITION CONTAINING A BISMUTH COMPOUND AND PROCESS FOR PREPARING THE SAME | |
| JPH11513354A (en) | Fast-curing hydroxyl-terminated polybutadiene binder system for gas generating compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE |
|
| 17P | Request for examination filed |
Effective date: 19940505 |
|
| 17Q | First examination report despatched |
Effective date: 19950829 |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE |
|
| REF | Corresponds to: |
Ref document number: 69305793 Country of ref document: DE Date of ref document: 19961212 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20070413 Year of fee payment: 15 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090101 |