EP0853603B1 - Schnellhärtendes Bindemittelsystem mit Hydroxylendgruppen enthaltende, geformte, gaserzeugende Zusammensetzungen und Verfahren zur Herstellung - Google Patents

Schnellhärtendes Bindemittelsystem mit Hydroxylendgruppen enthaltende, geformte, gaserzeugende Zusammensetzungen und Verfahren zur Herstellung Download PDF

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Publication number
EP0853603B1
EP0853603B1 EP96929767A EP96929767A EP0853603B1 EP 0853603 B1 EP0853603 B1 EP 0853603B1 EP 96929767 A EP96929767 A EP 96929767A EP 96929767 A EP96929767 A EP 96929767A EP 0853603 B1 EP0853603 B1 EP 0853603B1
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EP
European Patent Office
Prior art keywords
gas
generating composition
weight percent
hydroxyl
molded
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
Application number
EP96929767A
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English (en)
French (fr)
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EP0853603A4 (de
EP0853603A1 (de
Inventor
Robert S. Scheffee
Merlin W. Larimer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Atlantic Research Corp
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Atlantic Research Corp
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Filing date
Publication date
Application filed by Atlantic Research Corp filed Critical Atlantic Research Corp
Publication of EP0853603A1 publication Critical patent/EP0853603A1/de
Publication of EP0853603A4 publication Critical patent/EP0853603A4/de
Application granted granted Critical
Publication of EP0853603B1 publication Critical patent/EP0853603B1/de
Anticipated expiration legal-status Critical
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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
    • 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 inflators for devices such as protective passive restraints or "air bags” used in motor vehicles, escape slide chutes, life rafts, and the like. More particularly, the present invention relates to molded gas-generating compositions according to claim 8 which are used in inflators and a method according to claim 1.
  • Inflation is generally accomplished by means of a gas, such as air, nitrogen, carbon dioxide, helium, and the like which is stored under pressure and further pressurized and supplemented at the time of use by the addition of high temperature combustion gas products produced by the burning of a gas-generating composition.
  • a gas such as air, nitrogen, carbon dioxide, helium, and the like which is stored under pressure and further pressurized and supplemented at the time of use by the addition of high temperature combustion gas products produced by the burning of a gas-generating composition.
  • the inflation gases are solely produced by gas-generating compositions.
  • gas-generating compositions are incorporated into mechanical inflator devices in the form of powders, grains, pellets, or the like.
  • a particular convenient manner to incorporate gas-generating compositions into inflator devices is to form or mold the compositions into solid structures.
  • molded gas-generating components In order to be moldable they generally include binder components, some of which are suspected to produce hazardous combustion products.
  • binder components some of which are suspected to produce hazardous combustion products.
  • PVC polyvinyl chloride
  • PCB's polychlorinated biphenyls
  • the present invention is directed to the use in the method of claim 1 of moldable gas-generating compositions which do not include binder components which are suspected of producing harmful combustion products. More particularly, the present invention is directed to the use in the method of claim 1 of moldable gas-generating compositions which avoid the use of polyvinyl chloride (PVC) binders.
  • PVC polyvinyl chloride
  • Gas-generating compositions containing hydroxyl terminated polybutadiene are known from EP 0194180 for use in gun propellant, from US4184031 for use in vorket propellants and from EP 0685368 (prior art as defined in Ar 54(3) EPC) for use in hydrid air bag inflation systems.
  • Another object of the present invention is to use gas-generating compositions which can be injection molded or extruded.
  • a further object of the present invention is to use moldable gas-generating compositions which do not include polyvinyl chloride binder components.
  • a still further object of the present invention is to use moldable gas-generating compositions which include hydroxyl terminated polybutadiene (HTPB) binder systems.
  • HTPB hydroxyl terminated polybutadiene
  • a still further object of the present invention is to use moldable gas-generating compositions which can be quick cured.
  • a still further object of the present invention is to use moldable gas-generating compositions which can be cured in approximately 7 minutes or less.
  • a yet further object of the present invention is to provide a method of molding gas-generating compositions according to claim 1.
  • a yet further object of the present invention is to provide a method of molding gas-generating compositions which include hydroxyl terminated polybutadiene (HTPB) binder systems which can be quick cured.
  • HTPB hydroxyl terminated polybutadiene
  • the present invention provides a molded gas-generating composition according to claim 8 which includes:
  • the present invention further provides a method of forming a molded gas-generating according to claim 1 which comprises:
  • the present invention further provides an inflator for inflating emergency devices which inflator includes a molded gas-generating composition according to claim 8 that consists essentially of an oxidizer component and a hydroxyl-terminated polybutadiene binder component.
  • the present invention is directed to the use in the method of claim 1 of gas-generating compositions which, upon ignition, rapidly generate large amounts of gaseous reaction products.
  • the gas-generating compositions used in the present invention are moldable. In this regard, they can be prepared so as to have a suitable viscosity for injection molding, extrusion, or the like. After molding the composition can be cured to form solid structures
  • the gas-generating compositions are molded into solid shapes which are incorporated into mechanical inflator devices such as protective passive restraints or "air bags” used in motor vehicles, escape slide chutes, life rafts, or the like.
  • the present gas-generating compositions can be used in conjunction with inflator devices which primarily rely upon stored pressurized gas, and combustible gas-generating compositions to supplement the pressure of the stored gas at the time of use.
  • the present gas-generating compositions can be used as the primary source of gas used to inflate an inflation device.
  • the molded gas-generating compositions of the present invention can be ignited by a conventional initiator or ignitor.
  • a conventional initiator or ignitor For example, when used in conjunction with protective passive restraints or "air bags" used in motor vehicles, electric squibs which are activated upon a sensed impact of the motor vehicle can be used to ignite the gas-generating compositions.
  • the gas-generating compositions used in the present invention according to claim 8 include an oxidizer component, a binder component which serves as a fuel, a curing agent for the binder component, and a cure catalyst.
  • the essential components include the oxidizer component and the binder component.
  • the curing agent and cure catalyst can be considered essential components. However, it is to be understood that the cure catalyst is only necessary when one desired to quicken the curing rate of the compositions.
  • Suitable oxidizers which can be used in the gas-generating compositions include alkali metal chlorates, alkali metal perchlorates, and mixtures thereof. Examples of these oxidizers include sodium chlorate, potassium chlorate, lithium chlorate, sodium perchlorate, potassium perchlorate, and lithium perchlorate. Other oxidizers which can be use include alkaline earth metal perchlorates and ammonium perchlorate.
  • One oxidizer which has been found to be particularly useful for purposes of the present invention is potassium perchlorate.
  • the binder component used in the gas-generating compositions is a hydroxyl-terminated polybutadiene (HTPB).
  • HTPB hydroxyl-terminated polybutadiene
  • This binder functions as both a binder and a fuel component in the composition.
  • Hydroxyl-terminated polybutadiene has been found to be a desirable binder component since it does not produce hazardous compounds upon combustion.
  • a curing agent for the binder component is included in the gas-generating composition.
  • the curing agent causes the binder component to cure during the molding process.
  • Curing agents include isocyanates and diisocyanates, particularly di-polyfuncational diisocyanates.
  • exemplary curing agents include hexamethylene diisocyanate, poly phenylmethylene isocyanate, isophorone diisocyanate, dimeryl diisocyanate, and the like.
  • a cure catalyst is included in the gas-generating compositions.
  • the cure catalyst accelerates the curing speed of the gas-generating compositions so that they can be quick cured after molding.
  • the curing catalysts are selected from the group consisting of triphenylbismuth, dibutyltin dilaurate, and mixtures thereof.
  • the curing catalyst accelerates the curing of the gas-generating compositions so that they can be molded quickly.
  • the oxidizer component comprises about 83 to 95 weight percent of the gas-generating compositions
  • the binder component and the curing agent together comprise about 5 to 17 weight percent of the composition
  • the cure catalyst comprises about 0.025 to 0.5 weight percent of the composition.
  • the oxidizer component comprises about 85 to 90 weight percent of the gas-generating compositions
  • the binder component and the curing agent together comprise about 10 to 15 weight percent of the composition
  • the cure catalyst comprises about 0.025 to 0.5 weight percent of the composition.
  • the oxidizer component comprises about 88 weight percent of the gas-generating compositions
  • the binder component and the curing agent together comprise about 11.8 to 11.9 weight percent of the composition
  • the cure catalyst comprises about 0.1 to 0.2 weight percent of the composition.
  • the gas-generating compositions used in the present invention have a cure rate of less than 7 minutes and more typically between about 3 to 5 minutes, over a temperature range of about 93.3 to 190.6°C (200 to 375°F).
  • the curing rate of the gas-generating compositions used in the present invention is dependent upon the curing temperature, as one would expect. The fastest curing times are obtained at higher curing temperatures.
  • the upper limit of the curing temperature is just below the decomposition temperature of the composition. Therefore, for purposes of the present invention, the upper cure temperature should be limited to about 190.6°C (375°F)
  • a composition which included about 88 weight percent of the oxidizer component, about 11.8 to 11.9 weight percent of the binder component, and about 0.1 to 0.2 weight percent of the cure catalyst was found to have a curing rate of between about 3 to 5 minutes at 176.7°C (350°F).
  • the gas-generating compositions used in the present invention are prepared by mixing the individual components together.
  • the binder component and oxidizer component can be premixed together. It is preferred to add the curing agent and cure catalyst to the binder component and oxidizer component just prior to molding or extruding the composition so that the composition does not begin to cure prematurely.
  • the components can be mixed together utilizing conventional mixers, blenders, mills, etc. which are known to be useful for mixing pyrotechnic compositions.
  • an extrudable mass of the composition is prepared by mixing the components together.
  • the extrudable mass is then fed into an extruder, extruded and blocked as desired.
  • the extrudable mass is extruded, cut free and cured.
  • the viscosity of the mixed composition can be adjusted as necessary by incorporating a removable solvent such as ethyl acetate, acetone, ethyl alcohol, or mixtures thereof.
  • a removable solvent such as ethyl acetate, acetone, ethyl alcohol, or mixtures thereof.
  • the necessary viscosity for extrusion (or injection molding) can easily be determined based upon the specifications of the processing equipment used.
  • a preferred stabilizer used in the examples which follow includes Triphenylbismuth, Maleic Anhydride, and Magnesium Oxide used together in substantially equal proportions or about 2:1:1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Combustion & Propulsion (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Air Bags (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)

Claims (8)

  1. Verfahren zum Bilden einer geformten gaserzeugenden Zusammensetzung, geeignet zur Verwendung in Aufblaseinrichtungen, umfassend:
    Bilden einer formbaren gaserzeugenden Zusammensetzung, die einen Oxidationsmittelbestandteil enthält, ausgewählt aus der Gruppe, bestehend aus Alkalimetallchloraten, Alkalimetallperchloraten, Erdalkalimetallchloraten, Erdalkalimetallperchloraten, Ammoniumperchlorat und Gemischen davon, einem Hydroxyl-terminierten Polybutadienbindemittelbestandteil, einem Härter, ausgewählt aus der Gruppe, bestehend aus Isocyanaten, Diisocyanaten und Gemischen davon zu Härten des Hydroxyl-terminierten Polybutadienbindemittelbestandteils, und einen Härtungskatalysator, ausgewählt aus der Gruppe, bestehend aus Triphenylbismuth, Dibutylzinndilaurat und Gemischen davon zum Beschleunigen der Härtungsgeschwindigkeit des Hydroxyl-terminierten Polybutadienbindemittelbestandteils;
    Formen der formbaren gaserzeugenden Zusammensetzung durch Spritzgießen oder Extrudieren; und
    Härten der geformten gaserzeugenden Zusammensetzung.
  2. Verfahren zum Bilden einer geformten gaserzeugenden Zusammensetzung nach Anspruch 1, wobei die gaserzeugende Zusammensetzung eine Härtungsgeschwindigkeit von 5 Minuten oder weniger bei einer Temperatur von 93,3 bis 190,6°C (200 bis 375°F) aufweist.
  3. Verfahren zum Bilden einer geformten gaserzeugenden Zusammensetzung nach Anspruch 1, wobei die gaserzeugende Zusammensetzung weiterhin ein entfernbares Lösungsmittel aufweist.
  4. Verfahren zum Bilden einer geformten gaserzeugenden Zusammensetzung nach Anspruch 1, wobei die formbare gaserzeugende Zusammensetzung ungefähr 85 bis 95 Gew.-% der gaserzeugenden Zusammensetzung ausmacht, der Hydroxylterminierte Polybutadienbindemittelbestandteil und das Härtungsmittel zusammen ungefähr 5 bis 15 Gew.-% der gaserzeugenden Zusammensetzung ausmachen, und der Härtungskatalysator etwa 0,025 bis 0,5 Gew.-% der gaserzeugenden Zusammensetzung ausmacht.
  5. Verfahren zum Bilden einer geformten gaserzeugenden Zusammensetzung nach Anspruch 4, wobei die formbare gaserzeugende Zusammensetzung ungefähr 85 bis 90 Gew.-% der gaserzeugenden Zusammensetzung ausmacht, der Hydroxylterminierte Polybutadienbindemittelbestandteil und das Härtungsmittel zusammen ungefähr 10 bis 15 Gew.-% der gaserzeugenden Zusammensetzung ausmachen, und der Härtungskatalysator etwa 0,025 bis 0,5 Gew.-% der gaserzeugenden Zusammensetzung ausmacht.
  6. Verfahren zum Bilden einer geformten gaserzeugenden Zusammensetzung nach Anspruch 5, wobei die formbare gaserzeugende Zusammensetzung ungefähr 88 Gew.-% der gaserzeugenden Zusammensetzung ausmacht, der Hydroxylterminierte Polybutadienbindemittelbestandteil und das Härtungsmittel zusammen ungefähr 11,8 bis 11,9 Gew.-% der gaserzeugenden Zusammensetzung ausmachen, und der Härtungskatalysator etwa 0,01 bis 0,2 Gew.-% der gaserzeugenden Zusammensetzung ausmacht.
  7. Verfahren zum Bilden einer geformten gaserzeugenden Zusammensetzung nach Anspruch 6, wobei die gaserzeugende Zusammensetzung eine Härtungszeit von etwa 3 Minuten bei einer Temperatur von etwa 176,7°C (350°F) aufweist.
  8. Geformte gaserzeugende Zusammensetzung, erhältlich durch das Verfahren gemäß Anspruch 1.
EP96929767A 1995-10-03 1996-08-29 Schnellhärtendes Bindemittelsystem mit Hydroxylendgruppen enthaltende, geformte, gaserzeugende Zusammensetzungen und Verfahren zur Herstellung Expired - Lifetime EP0853603B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US53848795A 1995-10-03 1995-10-03
US538487 1995-10-03
PCT/US1996/013827 WO1997012846A1 (en) 1995-10-03 1996-08-29 Quick cure hydroxyl-terminated binder system for gas-generating compositions

Publications (3)

Publication Number Publication Date
EP0853603A1 EP0853603A1 (de) 1998-07-22
EP0853603A4 EP0853603A4 (de) 2000-11-22
EP0853603B1 true EP0853603B1 (de) 2003-12-03

Family

ID=24147121

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96929767A Expired - Lifetime EP0853603B1 (de) 1995-10-03 1996-08-29 Schnellhärtendes Bindemittelsystem mit Hydroxylendgruppen enthaltende, geformte, gaserzeugende Zusammensetzungen und Verfahren zur Herstellung

Country Status (6)

Country Link
EP (1) EP0853603B1 (de)
JP (1) JPH11513354A (de)
KR (1) KR19990044368A (de)
AU (1) AU6903996A (de)
DE (1) DE69630965T2 (de)
WO (1) WO1997012846A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2818636B1 (fr) 2000-12-22 2003-02-28 Poudres & Explosifs Ste Nale Compositions pyrotechniques generatrices de gaz a liant hydrocarbone et procede de fabrication en continu
JP5666105B2 (ja) * 2009-07-15 2015-02-12 株式会社Ｉｈｉエアロスペース ハイブリッドロケットの固体燃料

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3692495A (en) * 1970-06-19 1972-09-19 Thiokol Chemical Corp Gas generator
US4184031A (en) * 1976-11-11 1980-01-15 Thiokol Corporation Control of cure rate of polyurethane resins
US4944815A (en) * 1980-07-24 1990-07-31 The United States Of America As Represented By The Secretary Of The Navy Bonding agent for composite propellants
US4670068A (en) * 1981-02-19 1987-06-02 Hercules Incorporated Polyfunctional isocyanate crosslinking agents for propellant binders
NO831850L (no) * 1982-05-28 1997-02-26 Royal Ordnance Plc Fremgangsmåte for fremstilling av en formet gummiaktig drivmiddelladning for raketter og liknende
US4803019A (en) * 1984-02-10 1989-02-07 Morton Thiokol, Inc. Process for forming a liner and cast propellant charge in a rocket motor casing
FR2577919B1 (fr) * 1985-02-27 1987-02-20 Poudres & Explosifs Ste Nale Procede de fabrication sans solvant de produits pyrotechniques composites a liant thermodurcissable et produits ainsi obtenus, notamment poudres propulsives composites
US4597811A (en) * 1985-07-03 1986-07-01 The United States Of America As Represented By The Secretary Of The Army Prevention of unwanted cure catalysis in isocyanate cured binders
US4925909A (en) * 1988-10-26 1990-05-15 Japan As Represented By Director General, Technical Research And Development Institute, Japan Defense Agency Gas-generating agent for use in ducted rocket engine
USH934H (en) * 1990-07-09 1991-07-02 The United States Of America As Represented By The Secretary Of The Army Maleic anhydride adjunct to triphenylbismuthine to improve mechanical properties of hydroxy terminated binders
US5472532A (en) * 1993-06-14 1995-12-05 Thiokol Corporation Ambient temperature mix, cast, and cure composite propellant formulations
US5474625A (en) * 1993-12-16 1995-12-12 The United States Of America As Represented By The Secretary Of The Navy Desensitized solid rocket propellant formulation
US5486248A (en) * 1994-05-31 1996-01-23 Morton International, Inc. Extrudable gas generant for hybrid air bag inflation system

Also Published As

Publication number Publication date
WO1997012846A1 (en) 1997-04-10
AU6903996A (en) 1997-04-28
EP0853603A4 (de) 2000-11-22
DE69630965D1 (de) 2004-01-15
KR19990044368A (ko) 1999-06-25
JPH11513354A (ja) 1999-11-16
EP0853603A1 (de) 1998-07-22
DE69630965T2 (de) 2004-10-28

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